Onium salts and blocking agent dissociation catalysts for blocked isocyanates, blocked isocyanate compositions containing the blocking agent dissociation catalyst, thermosetting resin compositions, cured products, and methods for producing the same.

Abstract

The present invention provides a blocking agent dissociation catalyst for a blocked isocyanate, said blocking agent dissociation catalyst including an onium salt that is represented by formula (1). (1) (In the formula, n, R1, R2, R3, A, X, a, b, and Q+ are as defined in the description.)

Description

[Technical Field]

[0001] The present invention relates to onium salts and blocking agent dissociation catalysts for blocked isocyanates, blocked isocyanate compositions containing the blocking agent dissociation catalyst, thermosetting resin compositions, cured products, and methods for producing the same. [Background technology]

[0002] Blocked isocyanates are compounds obtained by reacting isocyanates with a blocking agent that has active hydrogen groups that can react with isocyanate groups. Blocked isocyanates have the property that the highly reactive isocyanate groups are encapsulated by the blocking agent, rendering them inactive at room temperature, and the blocking agent dissociates upon heating, regenerating the isocyanate groups. Due to these properties, blocked isocyanates have superior storage stability and are easier to handle compared to isocyanates. Taking advantage of these characteristics, they are widely used as raw materials for one-component polyurethane resins obtained by curing polyol components and isocyanate components, for example, in applications such as paints and adhesives.

[0003] As mentioned above, blocked isocyanates require heating to dissociate the blocking agent. However, in recent years, there has been a demand for lower dissociation temperatures of the blocking agent to reduce energy consumption and costs. Therefore, attempts have been made to use catalysts to lower the dissociation temperature of the blocking agent in blocked isocyanates. Organotin compounds such as dibutyltin dilaurylate are often used as such blocking agent dissociation catalysts, but their use is not desirable due to toxicity issues. Quaternary ammonium methyl carbonate is also known as a nonmetallic blocking agent dissociation catalyst (Patent Document 1). However, when the inventors used trimethyl-n-hexylammonium methyl carbonate, a quaternary ammonium methyl carbonate, as a blocking agent dissociation catalyst in a reaction between blocked isocyanates and polyols, the low-temperature curability was not satisfactory (see Comparative Example 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-222891 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention has been made in view of the above-mentioned background art, and aims to provide a catalyst that exhibits excellent low-temperature dissociation properties of the blocking agent of a blocked isocyanate. Furthermore, the present invention aims to provide a blocked isocyanate composition containing the blocking agent dissociation catalyst, a thermosetting resin composition containing the blocked isocyanate composition that exhibits excellent low-temperature curing properties, a cured product, and a method for producing the same. [Means for solving the problem]

[0006] The inventors of this invention conducted diligent research to solve the above problems and discovered that when an onium salt represented by formula (1) was used as a blocking agent dissociation catalyst for blocked isocyanates, it exhibited excellent low-temperature dissociation properties, thus completing the present invention.

[0007] The present invention provides the following blocking agent dissociation catalysts for blocked isocyanates, blocked isocyanate compositions, thermosetting resin compositions, cured products, methods for producing the same, and onium salts. [1] A blocking agent dissociation catalyst for blocked isocyanates containing an onium salt represented by the following formula (1). Formula (1):

[0008] [ka]

[0009] (In the formula, n is an integer greater than or equal to 1. R 1 , R 2 and R 3represents, independently of each other, a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group when n = 1, and represents a substituted or unsubstituted n-valent hydrocarbon group when n is an integer of 2 or more. R 1 , R 2 , and R 3 may be partially or entirely bonded to each other to form a ring structure. X represents a carbon atom, a nitrogen atom, or an oxygen atom. a represents 0 or 1. b represents 0 or 1. When X is a carbon atom, a = 1 and b = 1 are indicated. When X is a nitrogen atom, a = 1 and b = 0 are indicated. When X is an oxygen atom, a = 0 and b = 0 are indicated. Q + represents a cation.) [2] In formula (1), the block agent dissociation catalyst for blocked isocyanate according to [1], wherein Q + is an organic cation. [3] In formula (1), the block agent dissociation catalyst for blocked isocyanate according to [1] or [2], wherein Q + is an organic cation represented by the following formula (2) or the following formula (3). [[]]Formula (2):

[0010] [Chemical formula] [[]]

[0011] [[]](In the formula, R 4 , R 5 , R 6 and R 7 independently of each other represent a substituted or unsubstituted hydrocarbon group. R 4 , R 5 , R 6 and R 7 may be partially or entirely bonded to each other to form a ring structure. Y + represents a nitrogen cation or a phosphorus cation.) ' Formula (3):

[0012] [Chemical formula]

[0013] (In the formula, R 8 , R 10 and R 11 R represents identical or different substituted or unsubstituted hydrocarbon groups. 9 R indicates a substituted or unsubstituted hydrocarbon group. 8 , R 9 , R 10 and R 11 Some or all of them may be bonded to each other to form a ring structure. + (This indicates a nitrogen cation or a phosphorus cation.) [4] Y + The blocking agent dissociation catalyst for blocked isocyanates according to [3], wherein is a nitrogen cation, or the organic cation represented by formula (3) is an organic cation represented by formula (3-1) or formula (3-2). Formula (3-1):

[0014] [ka]

[0015] (In the formula, R 9 and R 12 R indicates a substituted or unsubstituted hydrocarbon group. 10 , R 13 and R 14 R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. 9 , R 10 , R 12 , R 13 and R 14 (Some or all of these may be bonded to each other to form a ring structure.) Formula (3-2):

[0016] [ka]

[0017] (In the formula, R 9 R indicates a substituted or unsubstituted hydrocarbon group.10 , R 15 , R 16 , R 17 and R 18 R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. 9 , R 10 , R 15 , R 16 , R 17 and R 18 (Some or all of these may be bonded to each other to form a ring structure.) [5] The blocking agent dissociation catalyst for blocked isocyanates according to [1], wherein A is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic aliphatic hydrocarbon group. [6] A blocking agent dissociation catalyst for blocked isocyanates according to any one of items [1] to [5], wherein n is an integer from 1 to 20. [7] If X is a carbon atom, then R 1 , R 2 and R 3 R is the same or different hydrogen atom, or a substituted or unsubstituted alkyl group, and when X is a nitrogen atom, 1 and R 2 R is the same or different hydrogen atom, or a substituted or unsubstituted alkyl group, and when X is an oxygen atom, 1 The blocking agent dissociation catalyst for blocked isocyanates according to any one of items [1] to [6], wherein is a substituted or unsubstituted alkyl group. [8] A blocked isocyanate composition containing a blocked isocyanate dissociation catalyst and a blocked isocyanate compound as described in any one of items [1] to [7]. [9] The blocked isocyanate composition according to [8], wherein the blocked isocyanate compound is a blocked isocyanate compound that has been blocked with at least one blocking agent selected from the group consisting of alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds.

[10] The blocked isocyanate composition according to [8] or [9], wherein the blocked isocyanate compound is a blocked isocyanate compound blocked with a fluoride alcohol compound.

[11] A thermosetting resin composition comprising a blocked isocyanate composition according to any one of items [8] to

[10] and a compound having an isocyanate-reactive group.

[12] The thermosetting resin composition according to

[11] , wherein the compound having an isocyanate reactive group is a polyol compound.

[13] A cured product obtained by curing the thermosetting resin composition described in

[11] or

[12] .

[14] A method for producing a cured product, comprising the step of heating and curing the thermosetting resin composition described in

[11] or

[12] .

[15] Onium salts represented by the following formula (1) (excluding 1,3-di-isopropyl-4,5-dimethylimidazolium N,N'-diphenylurate). Formula (1):

[0018] [ka]

[0019] (In the formula, n is an integer greater than or equal to 1. R 1 , R 2 , and R 3represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group when n=1, and a substituted or unsubstituted n-valent hydrocarbon group when n is an integer of 2 or more. 1 , R 2 , and R 3 Some or all of the atoms may be bonded to each other to form a ring structure. X represents a carbon atom, a nitrogen atom, or an oxygen atom. a represents 0 or 1. b represents 0 or 1. If X is a carbon atom, then a=1 and b=1. If X is a nitrogen atom, then a=1 and b=0. If X is an oxygen atom, then a=0 and b=0. Q + (This represents an organic cation represented by formula (2) or formula (3) below.) Formula (2):

[0020] [ka]

[0021] (In the formula, R 4 , R 5 , R 6 and R 7 R represents identical or different substituted or unsubstituted hydrocarbon groups. 4 , R 5 , R 6 and R 7 Some or all of them may be bonded to each other to form a ring structure. + This represents a nitrogen cation or a phosphorus cation. Formula (3):

[0022] [ka]

[0023] (In the formula, R 8 , R 10 , and R 11 R represents identical or different substituted or unsubstituted hydrocarbon groups. 9 R indicates a substituted or unsubstituted hydrocarbon group. 8 , R 9, R 10 , and R 11 may be partially or entirely bonded to each other to form a ring structure. Z + represents a nitrogen cation or a phosphorus cation. )

[16] Y + is a nitrogen cation, or the organic cation represented by formula (3) is the organic cation represented by formula (3-1) or formula (3-2), the onium salt described in

[15] . Formula (3-1):

[0024]

Chem.

[0025] (In the formula, R 9 and R 12 represent a substituted or unsubstituted hydrocarbon group. R 10 , R 13 and R 14 are the same or different and represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. R 9 , R 10 , R 12 , R 13 and R 14 [[ID=4 / 6]] may be partially or entirely bonded to each other to form a ring structure. ) Formula (3-2):

[0026]

Chem.

[0027] (In the formula, R 9 represents a substituted or unsubstituted hydrocarbon group. R 10 , R 15 , R 16 , R[[ID= / 70]] 17 and R 18 9 , R 10 , R 15 , R [[ID= / 80]] 16 , R 17 18(Some or all of these may be bonded to each other to form a ring structure.)

[17] The onium salt according to

[16] , wherein A is a hydrogen atom, a substituted or unsubstituted n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent alicyclic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, or a substituted or unsubstituted n-valent aromatic aliphatic hydrocarbon group.

[18] An onium salt described in any one of the items

[15] to

[17] , where n is an integer from 1 to 20.

[19] The onium salt according to

[15] , having one anion selected from (4-1) to (4-4) and one organic cation selected from (bi) or (b-ii). Formula (4-1):

[0028] [ka]

[0029] (In the formula, A 1 R indicates a substituted or unsubstituted aromatic hydrocarbon group. 1a (This indicates a substituted or unsubstituted aliphatic hydrocarbon group.) Formula (4-2):

[0030] [ka]

[0031] (In the formula, A 2 and R 1a (This indicates identical or different substituted or unsubstituted aliphatic hydrocarbon groups.) Formula (4-3):

[0032] [ka]

[0033] (In the formula, A 1 and R 1a(As defined above.) Formula (4-4):

[0034] [ka]

[0035] (In the formula, A 2 and R 1a (As defined above.) (bi) Organic cation represented by formula (2) Formula (2):

[0036] [ka]

[0037] (In the formula, R 4 , R 5 , R 6 and R 7 R represents identical or different substituted or unsubstituted hydrocarbon groups. 4 , R 5 , R 6 and R 7 Some or all of them may be bonded to each other to form a ring structure. + (This is a nitrogen cation.) (b-ii) Organic cation represented by the following formula (3-1) Formula (3-1):

[0038] [ka]

[0039] (In the formula, R 9 and R 12 R indicates a substituted or unsubstituted hydrocarbon group. 10 , R 13 and R 14 R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. 9 , R 10 , R 12 , R 13 and R14 (Some or all of these may be bonded to each other to form a ring structure.)

[20] The onium salt according to

[15] , having one anion selected from (ai) to (a-iv) and one organic cation selected from (bi) or (b-ii).

[0040] [ka]

[0041] (bi) Organic cation represented by formula (2) Formula (2):

[0042] [ka]

[0043] (In the formula, R 4 , R 5 , R 6 and R 7 R represents identical or different substituted or unsubstituted hydrocarbon groups. 4 , R 5 , R 6 and R 7 Some or all of them may be bonded to each other to form a ring structure. + (This is a nitrogen cation.) (b-ii) Organic cation represented by the following formula (3-1) Formula (3-1):

[0044] [ka]

[0045] (In the formula, R 9 and R 12 R indicates a substituted or unsubstituted hydrocarbon group. 10 , R 13 and R 14 R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. 9 , R10 , R 12 , R 13 and R 14 (Some or all of these may be bonded to each other to form a ring structure.) 〔twenty one〕 The onium salt described in

[15] , wherein the onium salt is one of the following:

[0046] [ka] [Effects of the Invention]

[0047] This invention provides a catalyst that exhibits excellent low-temperature dissociation properties of the blocking agent of blocked isocyanates. Furthermore, it provides a blocked isocyanate composition containing the blocking agent dissociation catalyst, a thermosetting resin composition containing the blocked isocyanate composition that exhibits excellent low-temperature curing properties, a cured product, and a method for producing the same. [Brief explanation of the drawing]

[0048] [Figure 1] The 1H-NMR analysis results for Manufacturing Example 8 of this application are shown. [Figure 2] The results of the IR analysis in manufacturing example 8 of this application are shown. [Figure 3] The 1H-NMR analysis results for manufacturing example A-10 of this application are shown. [Figure 4] The results of the IR analysis for manufacturing example A-10 of this application are shown. [Modes for carrying out the invention]

[0049] <Blocking agent dissociation catalyst for blocked isocyanates> As a blocking agent dissociation catalyst for blocked isocyanates in the present invention, an onium salt represented by formula (1) (hereinafter referred to as onium salt (1)) can be used. Formula (1):

[0050] [ka]

[0051] (In the formula, n is an integer greater than or equal to 1. R 1 , R 2 , and R 3 represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group when n=1, and a substituted or unsubstituted n-valent hydrocarbon group when n is an integer of 2 or more. 1 , R 2 , and R 3 Some or all of the atoms may be bonded to each other to form a ring structure. X represents a carbon atom, a nitrogen atom, or an oxygen atom. a represents 0 or 1. b represents 0 or 1. If X is a carbon atom, then a=1 and b=1. If X is a nitrogen atom, then a=1 and b=0. If X is an oxygen atom, then a=0 and b=0. Q + (This indicates a cation.) In equation (1), Q + Examples of cations represented by the formula are organic cations, preferably nitrogen-containing organic cations and organic phosphonium cations, more preferably organic cations represented by the following formula (2) or formula (3), even more preferably organic cations represented by the following formula (2), formula (3-1), or formula (3-2), and particularly preferably organic cations represented by the following formula (2) or formula (3-1). Formula (2):

[0052] [ka]

[0053] (In the formula, R 4 , R 5 , R 6 and R 7 R represents identical or different substituted or unsubstituted hydrocarbon groups. 4 , R 5 , R 6 and R 7 Some or all of them may be bonded to each other to form a ring structure.+ (This indicates a nitrogen cation or a phosphorus cation.) Formula (3):

[0054] [ka]

[0055] (In the formula, R 8 , R 9 , and R 11 R represents identical or different substituted or unsubstituted hydrocarbon groups. 10 R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. 8 , R 9 , R 10 , and R 11 Some or all of them may be bonded to each other to form a ring structure. + (This indicates a nitrogen cation or a phosphorus cation.) Formula (3-1):

[0056] [ka]

[0057] (In the formula, R 9 and R 12 R indicates a substituted or unsubstituted hydrocarbon group. 10 , R 13 and R 14 R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. 9 , R 10 , R 12 , R 13 and R 14 (Some or all of these may be bonded to each other to form a ring structure.) Formula (3-2):

[0058] [ka]

[0059] (In the formula, R 9represents a substituted or unsubstituted hydrocarbon group. R 10 、R 15 、R 16 、R 17 and R 18 are the same or different and represent a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. R 9 、R 10 、R 15 、R 16 、R 17 and R 18 may be partially or entirely bonded to each other to form a ring structure.) In the onium salt (1), as the anion, an anion represented by the formula (4) is preferable, an organic anion represented by the following formulas (4-1) to (4-4) is more preferable, and the following formulas (a-i) to (a-vi) are particularly preferable. Formula (4):

[0060]

Chemical formula

[0061] (In the formula, n, R 1 、R 2 、R 3 、A, a, b and X are as defined above.) Formula (4-1):

[0062]

Chemical formula

[0063] (In the formula, A 1 represents a substituted or unsubstituted aromatic hydrocarbon group. R 1a represents a substituted or unsubstituted aliphatic hydrocarbon group.) Formula (4-2):

[0064] ​​​​​​​​​​​​represents an aliphatic hydrocarbon group which may be the same or different and may be substituted or unsubstituted.) Formula (4-3):

[0066]

Chem.

[0067] (In the formula, A 1 , R 1a are as defined above.) Formula (4-4):

[0068]

Chem.

[0069] (In the formula, A 2 , R 1a are as defined above.) Formula (a-i):

[0070]

Chem.

[0071] Formula (a-ii):

[0072]

Chem.

[0073] Formula (a-iii):

[0074]

Chem.

[0075] Formula (a-iv):

[0076]

Chem.

[0077] Formula (a-v):

[0078]

Chem.

[0079] Formula (a-vi):

[0080]

Chem.

[0081] In one aspect, in Formula (1) and Formula (4), R 1 , R 2 and R 3 are a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. In another aspect, in Formula (1) and Formula (4), R 1 , R 2 and R 3 are a hydrogen atom, or a substituted or unsubstituted alkyl group, preferably a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

[0082] In another aspect, in Formula (1) and Formula (4), R 1 , R 2 and R 3The group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0083] In one embodiment, in formulas (1) and (4), A is a hydrogen atom or a substituted or unsubstituted n-valent hydrocarbon group, preferably a hydrogen atom, a substituted or unsubstituted n-valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, a substituted or unsubstituted n-valent aromatic hydrocarbon group having 6 to 200 carbon atoms, or a substituted or unsubstituted n-valent aromatic aliphatic hydrocarbon group having 7 to 200 carbon atoms. Furthermore, "n-valent hydrocarbon group" refers to the remaining group after n hydrogens have been removed from a hydrocarbon group; "n-valent aliphatic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an aliphatic hydrocarbon group; "n-valent alicyclic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an alicyclic hydrocarbon group; "n-valent aromatic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an aromatic hydrocarbon group; and "n-valent aromatic aliphatic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an aromatic aliphatic hydrocarbon group.

[0084] In this specification, "substituted or unsubstituted (n-valent) hydrocarbon group" includes (i) an (n-valent) hydrocarbon group which may have substituents, (ii) an (n-valent) hydrocarbon group which may be substituted with a heteroatom, and (iii) a hydrocarbon group which has substituents and is substituted with a heteroatom.

[0085] Furthermore, "substituted or unsubstituted aliphatic hydrocarbon groups" include (iv) aliphatic hydrocarbon groups that may have substituents (n-valent), (v) aliphatic hydrocarbon groups that may be substituted with heteroatoms (n-valent), and (vi) aliphatic hydrocarbon groups that have substituents and are substituted with heteroatoms (n-valent).

[0086] Furthermore, "substituted or unsubstituted (n-valent) alicyclic hydrocarbon groups" include (vii) alicyclic hydrocarbon groups that may have substituents (n-valent), (viii) alicyclic hydrocarbon groups that may be substituted with heteroatoms (n-valent), and (ix) alicyclic hydrocarbon groups that have substituents and are substituted with heteroatoms (n-valent).

[0087] Furthermore, "substituted or unsubstituted (n-valent) aromatic hydrocarbon groups" include (x) (n-valent) aromatic hydrocarbon groups which may have substituents, (xi) (n-valent) aromatic hydrocarbon groups which may be substituted with heteroatoms, and (xii) (n-valent) aromatic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0088] Furthermore, "substituted or unsubstituted (n-valent) aromatic aliphatic hydrocarbon groups" include (xiii) (n-valent) aromatic aliphatic hydrocarbon groups which may have substituents, (xiv) (n-valent) aromatic aliphatic hydrocarbon groups which may be substituted with heteroatoms, and (xv) (n-valent) aromatic aliphatic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0089] Examples of "unsubstituted hydrocarbon groups" include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, decyl group, dodecyl group, octadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, tolyl group, and allyl group.

[0090] Examples of "unsubstituted aliphatic hydrocarbon groups" include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, dodecyl, octadecyl, and allyl groups.

[0091] Examples of "unsubstituted alicyclic hydrocarbon groups" include cyclopropyl groups, cyclopentyl groups, and cyclohexyl groups.

[0092] Examples of "unsubstituted aromatic hydrocarbon groups" include phenyl groups and tolyl groups.

[0093] Examples of "unsubstituted aromatic aliphatic hydrocarbon groups" include benzyl groups, phenethyl groups, and xylylene groups.

[0094] In this specification, examples of "substituents" include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkylamino groups such as methylamino groups; dialkylamino groups such as dimethylamino groups; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenoxy and naphthyloxy groups; aralkyloxy groups such as benzyloxy and naphthylmethoxy groups; halogenated alkyl groups such as trifluoromethyl groups; nitro groups; cyano groups; sulfonyl groups; alkylcarbonylamino groups; alkyloxycarbonylamino groups; (alkylamino)carbonylamino groups; or (dialkylamino)carbonylamino groups. 1 , R 2 and R 3 The hydrocarbon group may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. R, R 2 and R 3 When the hydrocarbon group is substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has at least one of the following groups: -O-, -N<, -NH-, -S-, -SO2-, etc., and the hydrocarbon chain is interrupted by these groups.

[0095] Examples of the alkyl portion of the alkylamino group, dialkylamino group, alkoxy group, halogenated alkyl group, alkylcarbonylamino group, alkyloxycarbonylamino group, (alkylamino)carbonylamino group, and (dialkylamino)carbonylamino group include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, heptyl, octyl, and 2-ethylhexyl. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 or 2.

[0096] Examples of the aryl portion of the above-mentioned aryloxy group include aryl groups having 6 to 10 carbon atoms. Specifically, examples of aryl portions include phenyl groups and naphthyl groups.

[0097] Examples of the aralkyl portion of the above-mentioned aralkyloxy group include aralkyl groups having 7 to 12 carbon atoms. Specifically, examples of aralkyl groups include benzyl groups and naphthylmethyl groups.

[0098] In A, unsubstituted n-valent hydrocarbon groups include methane, ethane, propane, isopropane, butane, sec-butane, tert-butane, pentane, hexane, heptane, 2-ethylhexane, decane, dodecane, octadecane, cyclopropane, cyclopentane, cyclohexane, benzene, naphthalene, toluene, phenylethane, and propylene, from which n hydrogen atoms have been removed. In the case of toluene and phenylethane, one or both of the hydrogen atoms of the aromatic ring and / or the methyl group or ethyl group may be removed. However, if n is 2 or more, the removed hydrogen atoms are hydrogen atoms bonded to different carbon atoms.

[0099] In another form, A is a substituted or unsubstituted branched chain hydrocarbon group, preferably a substituted or unsubstituted chain hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted chain hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted chain hydrocarbon group having 1 to 30 carbon atoms.

[0100] Examples of "chain hydrocarbon groups" include branched alkyl groups, branched alkenyl groups, or branched alkynyl groups.

[0101] Examples of "chain-like hydrocarbon groups" include isopropyl groups and 2-ethylhexyl groups.

[0102] R, which will be discussed later 4 , R 5 , R 6 and R 7 However, in the case of an unsubstituted hydrocarbon group, particularly an unsubstituted alkyl group, cycloalkyl group, aryl group, or aralkyl group, and n=1, one mode in which A is a substituted or unsubstituted branched chain hydrocarbon group is preferred.

[0103] In yet another form, in formulas (1) and (4), A is the hydrocarbon group excluding the isocyanate group of the following isocyanates (i) to (v). In this specification, isocyanate includes monofunctional isocyanates and polyfunctional isocyanates. (i) Aliphatic isocyanates, (ii) Alicyclic isocyanates, (iii) Aromatic isocyanates, (iv) Aromatic aliphatic isocyanates, (v) A modified isocyanate formed from at least one selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, and aromatic aliphatic isocyanates.

[0104] In this specification, specific examples of preferred groups represented by A are given below.

[0105] [ka]

[0106] In formulas (1) and (4), X represents a carbon atom, a nitrogen atom, or an oxygen atom, preferably a nitrogen atom or an oxygen atom.

[0107] In formulas (1) and (4), n is an integer of 1 or more, preferably an integer between 1 and 20, more preferably between 1 and 6, even more preferably between 1 and 4, and particularly preferably 1 or 2.

[0108] In equations (4-1), (4-2), (4-3), and (4-4), A 1 This is a substituted or unsubstituted aromatic hydrocarbon group, preferably a substituted or unsubstituted aromatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aromatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms.

[0109] In equations (4-1), (4-2), (4-3), and (4-4), A 2 and R 1a is a substituted or unsubstituted aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0110] In formula (2), R 4 , R 5 , R 6 and R 7 This is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

[0111] Another example is R4 , R 5 , R 6 and R 7 The group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0112] In formula (2), Y + is a nitrogen cation (N + ) or phosphate cation (P + ) is preferably a nitrogen cation.

[0113] In formula (2), Y + If R is a nitrogen cation, 4 , R 5 , R 6 and R 7 At least one of these is preferably a hydrocarbon group having one or more substituents, independently selected from the group consisting of halogen atoms, alkyl halides, alkoxy groups, aryloxy groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, alkyloxycarbonylamino groups, aryloxycarbonylamino groups, monoalkylsiloxy groups, dialkylsiloxy groups, trialkylsiloxy groups, monoarylsiloxy groups, diarylsiloxy groups, triarylsiloxy groups, monoalkylsilyl groups, dialkylsilyl groups, trialkylsilyl groups, hydroxyl groups, nitro groups, and cyano groups, and is particularly preferably a hydrocarbon group having an alkoxy group.

[0114] Examples of organic cations represented by formula (2) include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraheptylammonium, tetraoctylammonium, tetranonylammonium, tetra(decyl)ammonium, N-ethyl-N,N,N-trimethylammonium, N,N,N-trimethyl-N-propylammonium, N-butyl-N,N,N-trimethylammonium, N-octyl-N,N,N-trimethylammonium, N,N,N-triethyl-N- Decylammonium, N,N,N-triethyl-N-eicosylammonium, N,N,N-tributyl-N-pentylammonium, N,N,N-tributyl-N-hexylammonium, N,N,N-tributyl-N-heptylammonium, N,N,N-tributyl-N-octylammonium, N,N,N-tributyl-N-nonylammonium, N,N,N-tributyl-N-decylammonium, N,N,N-tributyl-N-eicosylammonium, N,N-diethyl-N-methyl-N-propylammonium, N-butyl-N,N-diethyl-N-methylammonium, N,N-dimethylpyrrolidinium, N,N-dimethylpiperidinium, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium, N,N-di(2-methoxyethyl)-N,N-dimethylammonium, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium, Tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tetrapentylphosphonium, tetrahexylphosphonium, tetraheptylphosphonium, tetraoctylphosphonium, tetranonylphosphonium, tetra(decyl)phosphonium, tributyloctylphosphonium, tri-n-butyl-n-hexylphosphonium, tributyldodecylphosphonium, trihexyltetradecylphosphonium, trimethyl(2-methoxyethyl)phosphonium, diethyl(2-methoxyethyl)methylphosphonium Examples include triethyl(2-ethoxyethyl)phosphonium, diethylpropyl(2-ethoxyethyl)phosphonium, ethyl[2-(2-methoxyethoxy)ethyl]dimethylphosphonium, diethyl[2-(2-methoxyethoxy)ethyl]methylphosphonium, di(2-methoxyethyl)dimethylphosphonium, di(2-ethoxyethyl)dimethylphosphonium, P-[2-(2-methoxyethoxy)ethyl](2-methoxyethyl)dimethylphosphonium, (2-ethoxyethyl)[2-(2-methoxyethoxy)ethyl]dimethylphosphonium, and others.

[0115] Preferably, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium, N,N-di(2-methoxyethyl) -N,N-dimethylammonium, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium, tri-n-butyl-n-hexylphosphonium, and particularly preferably N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium and tri-n-butyl-n-hexylphosphonium.

[0116] In formula (3), R 8 , R 9 , and R 11 This is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

[0117] Another example is R 8 , R 9 and R 11The group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0118] In formula (3), R 10 This is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

[0119] Another example is R 10 This is a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0120] In equation (3), R 8 , R 9 , R 10 and R 11 Some or all of them may be bonded to each other to form a ring structure. For example, R 8 and R 11When these elements bond to each other to form a ring structure, they can take on structures such as those shown in formulas (3a), (3b), or (3c) below. Equation (3a), Equation (3b), Equation (3c):

[0121] [ka]

[0122] (In the formula, R 9 , R 10 As defined above, R d E represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. 1 , E 2 , E 3 (wherein G represents a substituted or unsubstituted divalent hydrocarbon group, and G represents an oxygen atom or a sulfur atom.) E 1 , E 2 , E 3 If is a divalent hydrocarbon group containing a substituent, it is preferable that the substituent is bonded to a carbon atom constituting the ring. 1 , E 2 , E 3 The number of substituents attached to it is one, two, or three.

[0123] E 1 , E 2 , E 3 In the case of a divalent hydrocarbon group, it may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. 1 , E 2 , E 3 When the hydrocarbon group is substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the divalent hydrocarbon group has at least one of the following groups: -O-, -N<, -NH-, -S-, etc., and the divalent hydrocarbon chain is interrupted by these groups.

[0124] R dIn this context, the substituted or unsubstituted hydrocarbon groups are preferably substituted or unsubstituted hydrocarbon groups having 1 to 100 carbon atoms, more preferably substituted or unsubstituted hydrocarbon groups having 1 to 50 carbon atoms, and particularly preferably substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms.

[0125] Another example is R d When is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0126] E 1 , E 2 , E 3 In this context, the substituted or unsubstituted divalent hydrocarbon group is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms.

[0127] Another example is E 1 , E 2 , E 3When is a substituted or unsubstituted divalent hydrocarbon group, the substituted or unsubstituted divalent hydrocarbon group is a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0128] The above is R 8 and R 11 This is an example of a case where R is bonded to each other to form a ring structure. 8 and R 9 , R 9 and R 10 , R 10 and R 11 Similarly, a ring structure can be formed when the elements bond to each other to form a ring structure.

[0129] The organic cation represented by formula (3) is preferably an organic cation represented by formula (3-1) or formula (3-2).

[0130] In formula (3-1), R 9 and R 12 This is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

[0131] Another example is R 9 and R 12The group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0132] In formula (3-1), R 10 , R 13 and R 14 This is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

[0133] Another example is R 10 , R 13 and R 14 This is a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0134] The organic cations represented by formula (3-1) include, specifically, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1-methyl-3-pentylimidazolium, 1-hexyl-3-methylimidazolium, 1-heptyl-3-methylimidazolium, 1-methyl-3-octylimidazolium, 1-methyl-3-nonylimidazolium, and 1- Sil-3-methylimidazolium, 1-allyl-3-methylimidazolium, 1-allyl-3-ethylimidazolium, 1-(2-methoxyethyl)-3-methylimidazolium, 1-(2-ethoxyethyl)-3-methylimidazolium, 1-ethyl-3-(2-methoxyethyl)imidazolium, 1-ethyl-3-(2-ethoxyethyl)imidazolium, 1,3-di(tert-butyl)imidazolium, 1,3-bis(1,1-dimethylethyl) Examples include imidazolium, 1,3-bis(1,1-dimethylpropyl)imidazolium, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium, 1,3-bis(1-methyl-1-phenylethyl)imidazolium, 1,3-bis(1,1-dimethyl-2-phenylethyl)imidazolium, 1,3-bis(1-adamantyl)imidazolium, and preferably 1,3-di(tert-butyl)imidazolium, 1,3-bis(1, These are 1-dimethylethyl)imidazolium, 1,3-bis(1,1-dimethylpropyl)imidazolium, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium, 1,3-bis(1-methyl-1-phenylethyl)imidazolium, 1,3-bis(1,1-dimethyl-2-phenylethyl)imidazolium, and 1,3-bis(1-adamantyl)imidazolium, with 1,3-di(tert-butyl)imidazolium being particularly preferred.

[0135] In formula (3-2), R 10 , R 15 , R 16 , R 17 and R 18This is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.

[0136] Another example is R 10 , R 15 , R 16 , R 17 and R 18 This is a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0137] Examples of organic cations represented by formula (3-2) include 1-methylpyridinium, 1-ethylpyridinium, 1-propylpyridinium, 1-butylpyridinium, 1-pentylpyridinium, 1-hexylpyridinium, 1-heptylpyridinium, 1-octylpyridinium, 1-nonylpyridinium, 1-decylpyridinium, 1-hexadecylpyridinium, 1-allylpyridinium, 1-(2-methoxyethyl)pyridinium, 1-(2-ethoxyethyl)pyridinium, and others, with 1-hexadecylpyridinium being preferred.

[0138] A keyA 1 , A 2 , R 1 ~R 18 , R 1a These may form a ring structure together with the carbon, oxygen, nitrogen, or phosphorus atoms to which they are bonded.

[0139] For example, R 13 and R 14 , R 17 and R 18 However, when they form a ring structure together with the carbon, oxygen, nitrogen, or phosphorus atoms to which they are bonded, they can take on a benzimidazolium ring structure or a quinolinium ring structure, for example, as shown in formula (3-1a) or formula (3-2a) below.

[0140] [ka]

[0141] (In the formula, R 9 , R 10 , R 12 , R 15 and R 16 This is as defined above. R w , R x , R y and R z Each of these represents either a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 9 (This may be an adamantyl group, particularly a 1-adamantyl group.) The above is R 13 and R 14 , R 17 and R 18 An example of a case where R forms a ring structure is shown below. 1 and R 2 , R 4 and R 5 , R 8 and R 9 , R 9 and R 10 , R 10 and R 12 , R 12 and R 13 , R 9 and R 14 , R 10 and R 15 , R 15 and R 16 Similarly, a ring structure can be formed in this case as well.

[0142] Specific examples of equation (1) include the following:

[0143] [Table 1]

[0144] [Table 2]

[0145] [Table 3]

[0146] [Table 4]

[0147] Preferred specific examples of the onium salt (1) of the present invention are shown below.

[0148] [ka]

[0149] Onium salt (1) can be produced, for example, by a method including (Step 2) described below. The compound represented by formula (6) used in Step 2 (hereinafter referred to as carbonate salt (6)) may be a commercially available product or obtained by a known method, or it can be produced, for example, by a method including (Step 1-1) or (Step 1-2) shown below.

[0150] (Step 1-1) The onium salt represented by formula (5) below is reacted with sodium carbonate or potassium carbonate, and the resulting sodium chloride or potassium chloride is removed to obtain the carbonate salt represented by formula (6-1) below (hereinafter referred to as carbonate salt (6-1)). The carbonate salt represented by formula (6-1) below corresponds to a compound in formula (6) where R is a hydrogen atom.

[0151] [ka]

[0152] (In the formula, X a This represents chloride ions, bromide ions, or iodide ions. Q + (As defined above.) (Step 1-2) The compound represented by formula (8) or (9) below is reacted with the carbonate ester represented by formula (11) (hereinafter referred to as carbonate ester (11)) to obtain the onium salt represented by formula (6-2) below (hereinafter referred to as carbonate salt (6-2)). The onium salt represented by formula (6-2) below has R in formula (6) 4 or R 9 This corresponds to the compound.

[0153] [ka]

[0154] (In the formula, R a R 4 or R 9 This indicates R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 Q + (Y and Z are as defined above.) (Step 2) The onium salt represented by formula (6) below is reacted with the compound represented by formula (7) below to obtain the onium salt represented by formula (1).

[0155] [ka]

[0156] (In the formula, R 1 , R 2 , R 3 Q + A, X, a, b, R a, and n are as defined above.

[0157] Formula (5):

[0158] [ka]

[0159] (In the formula, Q + X is defined as described above. a- (This represents chloride ions, bromide ions, or iodide ions.) Formula (6):

[0160] [ka]

[0161] (In the formula, R is a hydrogen atom, R 4 or R 9 This indicates Q + , R 4 and R 9 (As defined above.) Formula (7):

[0162] [ka]

[0163] (In the formula, R 1 , R 2 , R 3 (A, a, b, and n are as defined above.) (Step 1-1) will be explained.

[0164] A specific example of an onium salt represented by the above formula (5) is: N-octyl-N,N,N-trimethylammonium chloride, N,N,N-triethyl-N-methylammonium chloride, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium chloride, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium chloride, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium chloride, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium chloride, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium chloride, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium chloride, N,N-di(2-methoxyethyl)-N,N-dimethylammonium chloride, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium chloride, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium chloride, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium chloride, Tri-n-butyl-n-hexylphosphonium chloride, 1,3-di(tert-butyl)imidazolium chloride, 1,3-Bis(1,1-dimethylethyl)imidazolium chloride, 1,3-Bis(1,1-dimethylpropyl)imidazolium chloride, 1,3-Bis(1,1,3,3-tetramethylbutyl)imidazolium chloride, 1,3-Bis(1-methyl-1-phenylethyl)imidazolium chloride, 1,3-Bis(1,1-dimethyl-2-phenylethyl)imidazolium chloride, 1,3-Bis(1-adamantyl)imidazolium chloride 1-Hexadecylpyridinium chloride N-octyl-N,N,N-trimethylammonium bromide, N,N,N-triethyl-N-methylammonium bromide, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium bromide, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bromide, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium bromide, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium bromide, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium bromide, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium bromide, N,N-di(2-methoxyethyl)-N,N-dimethylammonium bromide, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium bromide, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium bromide, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium bromide, Tri-n-butyl-n-hexylphosphonium bromide, 1,3-di(tert-butyl)imidazolium bromide, 1,3-Bis(1,1-dimethylethyl)imidazolium bromide, 1,3-Bis(1,1-dimethylpropyl)imidazolium bromide, 1,3-Bis(1,1,3,3-tetramethylbutyl)imidazolium bromide, 1,3-Bis(1-methyl-1-phenylethyl)imidazolium bromide, 1,3-Bis(1,1-dimethyl-2-phenylethyl)imidazolium bromide, 1,3-Bis(1-adamantyl)imidazolium bromide 1-Hexadecylpyridinium bromide N-octyl-N,N,N-trimethylammonium iodide, N,N,N-triethyl-N-methylammonium iodide, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium iodide, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium iodide, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium iodide, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium iodide, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium iodide, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium iodide, N,N-di(2-methoxyethyl)-N,N-dimethylammonium iodide, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium iodide, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium iodide, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium iodide, Tri-n-butyl-n-hexylphosphonium iodide, 1,3-di(tert-butyl)imidazolium iodide, 1,3-Bis(1,1-dimethylethyl)imidazolium iodide, 1,3-Bis(1,1-dimethylpropyl)imidazolium iodide, 1,3-Bis(1,1,3,3-tetramethylbutyl)imidazolium iodide, 1,3-Bis(1-methyl-1-phenylethyl)imidazolium iodide, 1,3-Bis(1,1-dimethyl-2-phenylethyl)imidazolium iodide, 1,3-Bis(1-adamantyl)imidazolium iodide 1-Hexadecylpyridinium iodide These are some examples.

[0165] A specific example of a carbonate salt represented by formula (6-1), which corresponds to a compound in formula (6) where R is a hydrogen atom, is: N-octyl-N,N,N-trimethylammonium bicarbonate, N,N,N-triethyl-N-methylammonium bicarbonate, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium bicarbonate, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium bicarbonate, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium bicarbonate, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium bicarbonate, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium bicarbonate, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium bicarbonate, N,N-di(2-methoxyethyl)-N,N-dimethylammonium bicarbonate, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium bicarbonate, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium bicarbonate, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium bicarbonate, Tri-n-butyl-n-hexylphosphonium bicarbonate, 1,3-di(tert-butyl)imidazolium bicarbonate, 1,3-bis(1,1-dimethylethyl)imidazolium bicarbonate, 1,3-bis(1,1-dimethylpropyl)imidazolium bicarbonate, 1,3-Bis(1,1,3,3-tetramethylbutyl)imidazolium bicarbonate, 1,3-bis(1-methyl-1-phenylethyl)imidazolium bicarbonate, 1,3-Bis(1,1-dimethyl-2-phenylethyl)imidazolium bicarbonate, 1,3-Bis(1-adamantyl)imidazolium bicarbonate, 1-Hexadecylpyridinium bicarbonate These are some examples.

[0166] For every mole of onium salt represented by formula (5), typically 1 mole or more, preferably 1 to 2 moles, and particularly preferably 1 to 1.5 moles, of sodium carbonate or potassium carbonate is used.

[0167] The reaction temperature is typically between 0°C and 100°C, or the boiling point of the solvent. Preferably, it is between 10°C and 100°C, and more preferably between 20°C and 80°C.

[0168] The reaction time is typically 1 to 100 hours, preferably 1 to 20 hours.

[0169] Examples of solvents include tetrahydrofuran, ethyl acetate, methanol, ethanol, acetonitrile, toluene, and acetone. When using a solvent, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (4). Two or more solvents may be mixed and used as needed.

[0170] In step 1-1, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium, if necessary.

[0171] The obtained carbonate salt (6-1) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for step 2 without purification.

[0172] The onium salt represented by formula (5) may be a commercially available product. The onium salt represented by formula (5) may be obtained, for example, by a known method described below.

[0173] An onium salt represented by formula (5) can be obtained by reacting a compound represented by formula (8) or formula (9) below with a compound represented by formula (10) below.

[0174] Formula (8):

[0175] [ka]

[0176] (In the formula, R 5 , R 6 and R 7 (As defined above, Y is either a nitrogen atom or a phosphorus atom.) Formula (9):

[0177] [ka]

[0178] (In the formula, R 8 , R 10 and R 11 This is as defined above. Z is either a nitrogen atom or a phosphorus atom. Equation (10): R a X a (In the formula, R a R 4 or R 9 This indicates R 4 , R 9 and X a (As defined above.) In formula (8), Y represents a nitrogen atom or a phosphorus atom, preferably a nitrogen atom.

[0179] Specific examples of compounds represented by the above formula (8) include: Dimethyl-n-octylamine, Triethylamine, N,N-dimethyl-N-(2-methoxyethyl)amine, N,N-diethyl-N-(2-methoxyethyl)amine, N-ethyl-N-(2-methoxyethyl)-N-methylamine, N,N-diethyl-N-(2-ethoxyethyl)amine, N-ethyl-N-propyl-N-(2-ethoxyethyl)amine, N,N-diethyl-N-(2-ethoxyethyl)ammonium, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylamine, N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylamine, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]amine, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylamine, N,N-di(2-methoxyethyl)-N,N-dimethylamine, N,N-di(2-ethoxyethyl)-N-methylamine, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N-methylamine, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N-methylamine, Di-n-butyl-n-hexylphosphine These are some examples.

[0180] In formula (9), Z represents a nitrogen atom or a phosphorus atom, preferably a nitrogen atom. The compound represented by formula (9) is preferably the compound represented by the following formulas (9-1) or (9-2).

[0181] Formula (9-1):

[0182] [ka]

[0183] (In the formula, R 10 , R 12 , R 13 and R 14 (As defined above.) Formula (9-2):

[0184] [ka]

[0185] (In the formula, R 10 , R 15 , R 16 , R 17 and R 18 (As defined above.) Specific examples of compounds represented by formula (9-1) include 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butyl-3-methylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1-octylimidazole, 1-nonylimidazole, 1-decylimidazole, 1-alliimidazole, 1-(2-methoxyethyl)imidazole, 1-(2-ethoxyethyl)imidazole, 1-(tert-butyl)imidazole, 1-(1,1-dimethylethyl)imidazole, 1-(1,1-dimethylpropyl)imidazole, and 1(1,1 Examples include ,3,3-tetramethylbutyl)imidazole, 1-(1-methyl-1-phenylethyl)imidazole, 1(1,1-dimethyl-2-phenylethyl)imidazole, 1-(1-adamantyl)imidazole, and preferably 1-(tert-butyl)imidazole, 1-(1,1-dimethylethyl)imidazole, 1-(1,1-dimethylpropyl)imidazole, 1-(1,1,3,3-tetramethylbutyl)imidazole, 1-(1-methyl-1-phenylethyl)imidazole, 1-(1,1-dimethyl-2-phenylethyl)imidazole, and 1-(adamantyl)imidazole.

[0186] Specific examples of compounds represented by formula (9-2) include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, α-picoline, β-picoline, γ-picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, 2-butylpyridine, 3-butylpyridine, 4-butylpyridine, 2-tert-butylpyridine, 3-tert-butylpyridine, 4-tert-butylpyridine, 2-amylpyridine, 3-amylpyridine, 4-amylpyridine, 2-chloropyridine, 3-chloro Examples include pyridine, 4-chloropyridine, 2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, 2,4,6-collidine, 2,3,5-collidine, 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, 2-acetylpyridine, 3-acetylpyridine, 4-acetylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, quinoline, isoquinoline, 1-methylisoquinoline, etc., with pyridine being preferred.

[0187] (Step 1-2) will be explained.

[0188] Equation (11):

[0189] [ka]

[0190] (In the formula, R a R 4 or R 9 This indicates R 4 and R 9 (As defined above.) Specific examples of carbonate esters (11) include, for example, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, and dihexyl carbonate, and alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate. Preferably, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate are used, and dimethyl carbonate is particularly preferred.

[0191] In equation (6), R is R 4 or R 9 A specific example of a carbonate salt represented by formula (6-2) that corresponds to the compound is: N-octyl-N,N,N-trimethylammonium methylcarbonate, N,N,N-triethyl-N-methylammonium methyl carbonate, N,N,N-trimethyl-N-(2-methoxyethyl)ammonium methyl carbonate, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium methyl carbonate, N,N-diethyl-N-(2-methoxyethyl)-N-methylammonium ethyl carbonate, N,N,N-triethyl-N-(2-ethoxyethyl)ammonium ethyl carbonate, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammonium ethyl carbonate, N,N-diethyl-N-propyl-N-(2-ethoxyethyl)ammoniumpropyl carbonate, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium methyl carbonate, N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium ethyl carbonate, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium methyl carbonate, N,N-diethyl-N-[2-(2-methoxyethoxy)ethyl]-N-methylammonium ethyl carbonate, N,N-di(2-methoxyethyl)-N,N-dimethylammonium methyl carbonate, N,N-di(2-ethoxyethyl)-N,N-dimethylammonium methyl carbonate, N-[2-(2-methoxyethoxy)ethyl]-N-(2-methoxyethyl)-N,N-dimethylammonium methyl carbonate, N-(2-ethoxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-N,N-dimethylammonium methyl carbonate, Tri-n-butyl-n-hexylphosphonium butyl carbonate, These are some examples.

[0192] The reaction typically involves using 0.8 moles to an excess amount, preferably 1.0 to 1.5 moles, of the carbonate ester represented by formula (11) per mole of the compound represented by formula (8) or formula (9).

[0193] The reaction temperature is typically between 10°C and 100°C, or the boiling point of the solvent.

[0194] The reaction time is typically 1 to 100 hours, preferably 1 to 10 hours.

[0195] A solvent may or may not be used. As a solvent, an excess of carbonate ester (11) may be used, or other solvents such as tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone may be used. When a solvent is used, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (4). Two or more solvents may be mixed and used as needed.

[0196] (Step 2) will be explained.

[0197] The onium salt represented by formula (6) is reacted with the compound represented by formula (7) to obtain the onium salt represented by formula (1). In this reaction, CO2 and water or R are used. a The alcohol represented by OH is removed.

[0198] In formula (7), R 1 , R2 , R 3 A, a, b, and n are as defined above.

[0199] The compound represented by formula (7) is preferably the compound represented by the following formulas (7-1) to (7-4). Formula (7-1):

[0200] [ka]

[0201] (In the formula, A 1 , R 1a (As defined above.) Formula (7-2):

[0202] [ka]

[0203] (In the formula, A 2 and R 1a (As defined above.) Formula (7-3):

[0204] [ka]

[0205] (In the formula, A 1 and R 1a (As defined above.) Formula (7-4):

[0206] [ka]

[0207] (In the formula, A 2 and R 1a (As defined above.) Specific examples of compounds represented by formula (7) include the following compounds. In the following examples, Ph represents a phenyl group, Me represents a methyl group, Et represents an ethyl group, Bu represents an n-butyl group, Hex represents an n-hexyl group, cHex represents a cyclohexyl group, and TFEt represents a 1,1,1-trifluoroethyl group.

[0208] [ka]

[0209] [ka]

[0210] [ka]

[0211] Particularly preferred are the following compounds. (a-i'):

[0212] [ka]

[0213] (a-ii'):

[0214] [ka]

[0215] (a-iii'):

[0216] [ka]

[0217] (a-iv'):

[0218] [ka]

[0219] For every mole of the onium salt represented by formula (6), approximately 1 mole, preferably 0.8 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles, of the compound represented by formula (7) is typically used.

[0220] The reaction temperature is typically 0 to 100°C or the boiling point of the solvent, preferably 10 to 80°C, more preferably 10 to 70°C.

[0221] The reaction time is typically 0.5 to 100 hours, preferably 1 to 10 hours.

[0222] Examples of solvents include tetrahydrofuran, ethyl acetate, methanol, ethanol, acetonitrile, toluene, and acetone. When using a solvent, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (4). Two or more solvents may be mixed and used as needed.

[0223] In step 1-2, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium, if necessary.

[0224] The obtained carbonate salt (6-2) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for step 2 without purification.

[0225] The compound represented by formula (7) may be a commercially available compound or one obtained by known methods. For example, in the case of (I) X=N or O, and (II) X=C, it can be obtained as follows.

[0226] [ka]

[0227] (In the formula, A, R 1 , R 2 , R3 a, b, and n are as defined above. X b (This represents OH, OCH3, OC2H5, or O- (succinimide).) (I) When X = N (nitrogen atom) or O (oxygen atom), the compound represented by formula (7) can be obtained by using n moles or an excess amount of the compound represented by formula (13) for 1 mole of the isocyanate compound represented by formula (12), and reacting the mixture in the presence of a solvent as needed at a temperature ranging from 10°C to the boiling point of the solvent for 1 to 24 hours. Examples of solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone. (II) When X = C (carbon atom), the compound represented by formula (7) can be obtained by using n moles or an excess amount of the compound represented by formula (15) for 1 mole of the amine compound represented by formula (14), and reacting the mixture in the presence of a solvent as needed at a temperature ranging from 10°C to the boiling point of the solvent for 1 to 24 hours. Examples of solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone.

[0228] Specific examples of isocyanate compounds represented by formula (12) are shown below. However, the present invention is not limited to these.

[0229] [ka]

[0230] (In equation (12-9), x is an integer between 0 and 20, preferably between 1 and 20.)

[0231] [ka]

[0232] [ka]

[0233] [ka]

[0234] The isocyanate compound represented by formula (12) is preferably the compound represented by (12-1), (12-2), (12-6), and (12-14), and is particularly preferably (12-1), (12-2), and (12-14).

[0235] Specific examples of compounds represented by formula (13) include phenols such as phenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; and alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol.

[0236] Specific examples of amine compounds represented by formula (14) are shown below. However, the present invention is not limited to these.

[0237] [ka]

[0238] (In equation (14-9), x is an integer between 0 and 20, preferably between 1 and 20.) The amine compound represented by formula (14) is preferably the compound represented by (14-1), (14-2), or (14-6), and particularly preferably (14-1) or (14-2).

[0239] Specific examples of compounds represented by formula (15) include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, capric acid, lauric acid, tetradecylic acid, palmitic acid, octadecylic acid, cyclohexanoic acid, ethoxyacetic acid, propoxyacetic acid, 2-(2-methoxyethoxy)acetic acid, 2-(2-ethoxyethoxy)acetic acid, 2-(2-propoxyethoxy)acetic acid, 3-methoxypropanoic acid, 3-ethoxypropanoic acid, 3-(2-methoxyethoxy)propanoic acid, 3-(2-ethoxyethoxy) Examples of carboxylic acids include propanoic acid, 3-(2-propoxyethoxy)propanoic acid, 3-(3-methoxypropoxy)propanoic acid, 3-(3-ethoxypropoxy)propanoic acid, 3-(3-propoxypropoxy)propanoic acid, oleic acid, linoleic acid, sorbic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, salicylic acid, trifluoroacetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid, adipic acid, fumaric acid, maleic acid, 1,7-heptanedicarboxylic acid, 1,10-decanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Preferably, the carboxylic acid is formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, or 2-ethylhexanoic acid, and more preferably acetic acid. Furthermore, it is an ester having an OCH3, OC2H5, or O-(succinimide) group derived from the above carboxylic acid.

[0240] The compound represented by formula (6) is, in formula (6), Q + If is an onium salt which is a cation represented by formula (3-1), it can be manufactured not only by the method via (step 1-1) or (step 1-2) above, but also by, for example, the following step 3. Step 3:

[0241] [ka]

[0242] (In the formula, R a , R 9 , R 10 , R 12, R 13 , R 14 , R 19 (As defined above.) When the imidazolium carboxylate represented by formula (20-1) (hereinafter referred to as imidazolium carboxylate (20-1)) is reacted with the carbonate ester (11), R in formula (6) becomes R a Q + A compound in which is an organic cation represented by formula (3-1) (hereinafter referred to as carbonate salt (6-2a)) is produced. a The same applies as above.

[0243] Carbonate salt (6-2a) can also be used as a raw material in step 2, but if necessary, step 4 below may be carried out, in formula (6) where R is a hydrogen atom, Q + A compound in which is an organic cation represented by formula (3-1) (hereinafter referred to as carbonate salt (6-1a)) can also be used as carbonate salt (6) in step 2. Step 4:

[0244] [ka]

[0245] (In the formula, R a , R 9 , R 10 , R 12 , R 13 , R 14 (As defined above.) The carbonate salt (6-2a) is reacted with water to obtain the carbonate salt (6-1a).

[0246] Let's explain step 3.

[0247] The imidazolium carboxylate salt represented by formula (20-1), which is used as a raw material, may be a commercially available product or one manufactured by a known method, but it can also be manufactured by the method described later.

[0248] In step 3, the amount of carbonate ester (11) used is usually 1 to 10 moles, preferably 1 to 3 moles, per mole of imidazolium carboxylate (20-1).

[0249] The reaction temperature is typically between 10°C and 120°C, or the boiling point of the solvent.

[0250] The reaction time is typically 1 to 20 hours, preferably 1 to 10 hours.

[0251] Carbonate ester compound (7) may be used in excess as a solvent, but other solvents may also be used. Other solvents include methanol, tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone. When using a solvent, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (4). Two or more solvents may be mixed and used as needed.

[0252] If necessary, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium.

[0253] After the reaction is complete, the carbonate salt (6-2a) can be obtained by removing impurities (e.g., unreacted raw materials) by washing with an organic solvent or by concentrating the reaction solution. If necessary, purification such as recrystallization may be performed. Let's explain step 4.

[0254] The amount of water used is usually 1 mole or more, preferably 1 to 10 moles, per mole of carbonate salt (6-2a). Water can also be used in excess as a reaction solvent.

[0255] The reaction temperature when reacting the carbonate salt (6-2a) with water is usually 10°C or higher, preferably 10°C to 100°C, and more preferably 10°C to 80°C.

[0256] The reaction time is typically 0.1 to 10 hours, preferably 0.1 to 5 hours.

[0257] Water can be used as a solvent, but if a solvent other than water is used, examples of such solvents include methanol, tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone. The amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (4). Two or more solvents can be mixed and used as needed.

[0258] If necessary, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium.

[0259] The obtained carbonate salt (6-1a) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for step 2 without purification.

[0260] The imidazolium carboxylate salt represented by formula (20-1) used in step 3 can be produced by the following method.

[0261] A dicarbonyl compound represented by formula (16) below, an amine compound represented by formulas (17x) and (17y) below, an aldehyde represented by formula (18) below, and a monovalent aliphatic carboxylic acid such as acetic acid represented by formula (19) below are reacted to obtain an imidazolium carboxylate salt represented by formula (20-1) below (hereinafter referred to as imidazolium carboxylate salt (20-1)).

[0262] [ka]

[0263] (In the formula, R 9 , R 10 , R 12 , R 13 , R 14 and R 19 (As defined above.) The dicarbonyl compound represented by formula (16) (hereinafter referred to as dicarbonyl compound (16)) is preferably glyoxal, diacetyl, 3,4-hexanedione, 2,3-pentanedione, 2,3-heptanedione, 5-methyl-2,3-hexanedione, 3-methyl-2,3-cyclopentanedione, 1,2-cyclohexanedione, 1-phenyl-1,2-propanedione, and dibenzoyl, more preferably glyoxal and diacetyl, and more preferably glyoxal.

[0264] Examples of amine compounds represented by formula (17x) (hereinafter referred to as amine compound (17x)) and amine compounds represented by formula (17y) (hereinafter referred to as amine compound (17y)) include tert-butylamine, 1,1,3,3-tetramethylbutylamine, and 1-adamantylamine, with 1,1,3,3-tetramethylbutylamine being preferred.

[0265] Examples of aldehydes represented by formula (18) include aliphatic, alicyclic, or aromatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.

[0266] The monovalent aliphatic carboxylic acids represented by formula (19) (hereinafter referred to as aliphatic carboxylic acids (19)) include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, capric acid, lauric acid, tetradecylic acid, palmitic acid, octadecylic acid, cyclohexanoic acid, ethoxyacetic acid, propoxyacetic acid, 2-(2-methoxyethoxy)acetic acid, 2-(2-ethoxyethoxy)acetic acid, 2-(2-propoxyethoxy)acetic acid, 3-methoxypropanoic acid, 3-ethoxypropanoic acid, 3-(2-methoxyethoxy)propane Examples of carboxylic acids include acids, 3-(2-ethoxyethoxy)propanoic acid, 3-(2-propoxyethoxy)propanoic acid, 3-(3-methoxypropoxy)propanoic acid, 3-(3-ethoxypropoxy)propanoic acid, 3-(3-propoxypropoxy)propanoic acid, oleic acid, linoleic acid, sorbic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, salicylic acid, and trifluoroacetic acid. Preferably, the carboxylic acid is formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, or 2-ethylhexanoic acid, and more preferably acetic acid.

[0267] Specific examples of imidazolium carboxylate salts (20-1) include, for example, 1,3-dimethylimidazolium formate, 1-ethyl-3-methylimidazolium formate, 1-butyl-3-methylimidazolium formate, 1-methyl-3-octylimidazolium formate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-methyl-3-(2-ethylhexyl)imidazolium formate, 1-dodecyl-3-methylimidazolium formate, and 1-methyl Tyl-3-octadecylimidazolium formate, 1-benzyl-3-methylimidazolium formate, 1,3-dibutylimidazolium formate, 1-butyl-3-ethylimidazolium formate, 1-butyl-3-octylimidazolium formate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-butyl-3-(2-ethylhexyl)imidazolium formate, 1-butyl-3-dodecylimidazolium formate, 1-butyl-3-octadecylimidazolium formate Silimidazolium formate, 1-benzyl-3-butylimidazolium formate, 1,3-dioctylimidazolium formate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-ethyl-3-octylimidazolium formate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-octyl-3-(2-ethylhexyl)imidazolium formate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium formate, Tylhexyl)imidazolium formate, 1-dodecyl-3-octylimidazolium formate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-octyl-3-octadecylimidazolium formate, 1-(1,1,3,3-tetramethylbutyl)-3-octadecylimidazolium formate, 1-benzyl-3-octylimidazolium formate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1,3-Bis(2-ethylhexyl)imidazolium formate, 1-ethyl-3-(2-ethylhexyl)imidazolium formate, 1-(2-ethylhexyl)-3-dodecylimidazolium formate, 1-(2-ethylhexyl)-3-octadecylimidazolium formate, 1-benzyl-3-(2-ethylhexyl)imidazolium formate, 1,3-didodecylimidazolium formate, 1-dodecyl-3-octadecylimidazolium formate, 1,3-benzyl-3-dodecylimidazolium formate, 1,3-dioctadecylimidazolium formate, 1,3-benzyl-3-octadecylimidazolium formate, 1,3-dibenzylimidazolium formate; 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-methyl-3-octylimidazolium acetate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-methyl-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-methylimidazolium acetate, 1-methyl-3-octadecylimidazolium acetate, 1-benzyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1-Butyl-3-ethylimidazolium acetate, 1-Butyl-3-octylimidazolium acetate, 1-Butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-Butyl-3-(2-ethylhexyl)imidazolium acetate, 1-Butyl-3-dodecylimidazolium acetate, 1-Butyl-3-octadecylimidazolium acetate, 1-benzyl-3-butylimidazolium acetate, 1,3-dioctylimidazolium acetate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate Salts, 1-ethyl-3-octylimidazolium acetate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3-(2-ethylhexyl)imidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3-octadecylimidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)imidazolium acetate Methylbutyl)-3-octadecylimidazolium acetate, 1-benzyl-3-octylimidazolium acetate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1,3-bis(2-ethylhexyl)imidazolium acetate, 1-ethyl-3-(2-ethylhexyl)imidazolium acetate, 1-(2-ethylhexyl)-3-dodecylimidazolium acetate, 1-(2-ethylhexyl)-3-octadecylimidazolium acetate, 1-benzyl-3-(2-ethylhexyl)imidazolium acetate, 1,3-Didodecylimidazolium acetate, 1-Dodecyl-3-Octadecylimidazolium acetate, 1-Benzyl-3-Dodecylimidazolium acetate, 1,3-Dioctadecylimidazolium acetate, 1-Benzyl-3-Octadecylimidazolium acetate, 1,3-Dibenzylimidazolium acetate; 1,3-dimethylimidazolium 2-ethylhexanoate, 1-ethyl-3-methylimidazolium 2-ethylhexanoate, 1-butyl-3-methylimidazolium 2-ethylhexanoate, 1-methyl-3-octylimidazolium 2-ethylhexanoate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-methyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-methylimidazolium 2-ethylhexanoate , 1-methyl-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-methylimidazolium 2-ethylhexanoate, 1,3-dibutylimidazolium 2-ethylhexanoate, 1-butyl-3-ethylimidazolium 2-ethylhexanoate, 1-butyl-3-octylimidazolium 2-ethylhexanoate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-butyl-3-(2-ethylhexyl)imidazolium 2-ethylhex Sodium phosphate, 1-butyl-3-dodecylimidazolium 2-ethylhexanoate, 1-butyl-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-butylimidazolium 2-ethylhexanoate, 1,3-dioctylimidazolium 2-ethylhexanoate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-ethyl-3-octylimidazolium 2-ethylhexanoate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium Dazolium 2-ethylhexanoate, 1-octyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-octylimidazolium 2-ethylhexanoate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-octyl-3-octadecylimidazolium 2-ethylhexanoate, 1-(1,1,3,3-Tetramethylbutyl)-3-Octadecylimidazolium 2-ethylhexanoate, 1-Benzyl-3-Octylimidazolium 2-ethylhexanoate, 1-Benzyl-3-(1,1,3,3-Tetramethylbutyl)imidazolium 2-ethylhexanoate, 1,3-Bis(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-Ethyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-(2-ethylhexyl)-3-dodecylimidazolium 2-ethylhexanoate, 1-(2-ethylhexyl)-3-O 1,3-Didodecylimidazolium 2-ethylhexanoate, 1-Benzyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1,3-Didodecylimidazolium 2-ethylhexanoate, 1-Dodecyl-3-Octadecylimidazorium 2-ethylhexanoate, 1-Benzyl-3-Dodecylimidazolium 2-ethylhexanoate, 1,3-Dioctadecylimidazolium 2-ethylhexanoate, 1,3-Benzyl-3-Octadecylimidazorium 2-ethylhexanoate, 1,3-Dibenzylimidazorium 2-ethylhexanoate; Examples include 1,3-dimethylbenzimidazolium formate, 1,3-dimethylbenzimidazolium acetate, and 1,3-dimethylbenzimidazolium 2-ethylhexanoate.

[0268] The imidazolium carboxylate salt (1) is preferably 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-methyl-3-octylimidazolium acetate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-methyl-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-methylimidazolium acetate, 1-benzyl-3-methylimidazolium acetate, 1,3- Dibutylimidazolium acetate, 1-butyl-3-ethylimidazolium acetate, 1-butyl-3-octylimidazolium acetate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-butyl-3-(2-ethylhexyl)imidazolium acetate, 1-butyl-3-dodecylimidazolium acetate, 1-benzyl-3-butylimidazolium acetate, 1,3-dioctylimidazolium acetate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate Salts, 1-ethyl-3-octylimidazolium acetate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3-(2-ethylhexyl)imidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-benzyl-3-octylimidazolium acetate These are 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1,3-bis(2-ethylhexyl)imidazolium acetate, 1-ethyl-3-(2-ethylhexyl)imidazolium acetate, 1-(2-ethylhexyl)-3-dodecylimidazolium acetate, 1-benzyl-3-(2-ethylhexyl)imidazolium acetate, 1,3-didodecylimidazolium acetate, 1-benzyl-3-dodecylimidazolium acetate, and 1,3-dibenzylimidazolium acetate.

[0269] The dicarbonyl compound (16) may be used as an aqueous solution or as an alcohol solution such as methanol or butanol.

[0270] The amount of amine compound (17x) and amine compound (17y) used (hereinafter, amine compound (17x) and amine compound (17y) together are referred to as amine compound (17)) is usually 0.1 to 10 moles, preferably 0.5 to 3 moles, of amine compound (17) per mole of dicarbonyl compound (16). Two moles of amine compound (17) react with one mole of dicarbonyl compound (16) to form one mole of imidazolium carboxylate (20-1). However, if, for example, less than two moles of amine compound (17) are used, in addition to the target imidazolium carboxylate (20-1), there will be dicarbonyl compound (16) (raw material) and polymers of dicarbonyl compound (16). Furthermore, if more than two moles of amine compound (17) are used per mole of dicarbonyl compound (16), there will be an excess amount of amine compound (16) in addition to the target imidazolium carboxylate (20-1). Imidazolium carboxylate salts (20-1) containing compounds other than these imidazolium cations can also be used as raw materials in step 3.

[0271] The ratio of amine compound (17x) to amine compound (17y) is not particularly limited, and is in the range of amine compound (17x):amine compound (17y) = 0:100 to 100:0. Note that in the case of amine compound (17x):amine compound (17y) = 0:100 or amine compound (17x):amine compound (17y) = 100:0, R 9 =R 12 It will become.

[0272] When using formaldehyde as aldehyde (18), the formaldehyde may be used as an aqueous solution or as an alcohol solution such as methanol or butanol. The amount of aldehyde (18) used is usually 0.1 to 10 moles, preferably 0.5 to 5.0 moles, of aldehyde (18) per mole of dicarbonyl compound (16).

[0273] The amount of monovalent aliphatic carboxylic acid (19), such as acetic acid, used is typically 0.1 to 10 moles, preferably 0.5 to 2 moles, and more preferably 1 to 1.5 moles, per mole of dicarbonyl compound (16).

[0274] The optimal reaction temperature varies depending on the raw materials and solvent used, but it is usually above -10°C, preferably between 0°C and 100°C. The reaction time is usually between 0.1 and 48 hours, preferably between 0.5 and 12 hours.

[0275] The solvent may or may not be used. If a solvent is used, the solvent is not particularly limited as long as it does not affect the reaction. Specific examples of solvents include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic or alicyclic hydrocarbons such as methylcyclohexane, cyclohexane, hexane, heptane, and octane; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; lower alcohols such as methanol and ethanol; N,N-dimethylformamide, acetonitrile, and water. Preferably, the solvent is aromatic hydrocarbon, lower alcohol, or water, and particularly preferably toluene or water. Two or more solvents may be mixed and used as needed.

[0276] The amount of solvent used is usually 50 parts by mass or less, preferably 0.1 to 10 parts by mass, per 1 part by mass of the dicarbonyl compound (16).

[0277] If necessary, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium.

[0278] After the reaction is complete, the imidazolium carboxylate (20-1) can be obtained by removing impurities (e.g., unreacted starting materials) by washing with an organic solvent or by concentrating the reaction solution. If necessary, purification such as recrystallization may be performed. <Blocked isocyanate composition containing a blocked isocyanate compound and an onium salt represented by formula (1)> The blocked isocyanate composition of the present invention comprises a blocked isocyanate compound together with an onium salt represented by formula (1).

[0279] Examples of blocked isocyanate compounds include compounds obtained by reacting an isocyanate with a blocking agent, thereby encapsulating the isocyanate groups in the isocyanate with the blocking agent. Blocked isocyanate compounds may be single compounds or mixtures of two or more types.

[0280] The isocyanates constituting the blocked isocyanate compound are not particularly limited as long as they are compounds having two or more isocyanate groups, but examples of isocyanates include the following: (i) Aliphatic isocyanates, (ii) Alicyclic isocyanates, (iii) Aromatic isocyanates, (iv) Aromatic aliphatic isocyanates, (v) A modified isocyanate formed from at least one selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, and aromatic aliphatic isocyanates.

[0281] Preferably, the modified isocyanate is formed from (i) an aliphatic isocyanate, (ii) an alicyclic isocyanate, and (v) at least one selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, and aromatic aliphatic isocyanates.

[0282] These isocyanates may be used individually or as a mixture of two or more.

[0283] Examples of aliphatic isocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate.

[0284] Examples of alicyclic isocyanates include 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate (IPDI)), bis-(4-isocyanatocyclohexyl)methane, and norbornane diisocyanate.

[0285] Examples of aromatic isocyanates include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1,4-phenylenediisocyanate, 2,4-tolinediisocyanate, 2,6-tolinediisocyanate, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylenediisocyanate.

[0286] Examples of aromatic aliphatic isocyanates include 1,3-xylylenediisocyanate, 1,4-xylylenediisocyanate, and α,α,α',α'-tetramethylxylylenediisocyanate.

[0287] Examples of modified isocyanates include isocyanate-terminated compounds and / or reaction products of the isocyanate-terminated compounds obtained by the reaction of the above-mentioned isocyanate compound with a compound having an active hydrogen group (for example, adduct-type isocyanates, isocyanate modified products obtained by allophanate reaction, carbodiimide reaction, uretdione reaction, isocyanurate reaction, uretonimination reaction, biuret reaction, etc.), with adduct-type isocyanates, isocyanates modified by isocyanurate reaction, and isocyanates modified by biuret reaction (isocyanates having biuret bonds) being preferred.

[0288] Isocyanates containing biuret bonds are obtained by reacting an isocyanate with a so-called biuretizing agent such as water, tert-butanol, or urea, in a molar ratio of isocyanate groups between the biuretizing agent and the isocyanate, at a ratio of approximately 1 / 2 to 1 / 100, followed by removal of unreacted isocyanate and purification. Isocyanates containing isocyanurate bonds are obtained, for example, by carrying out a cyclic trimerization reaction using a catalyst, stopping the reaction when the conversion rate reaches approximately 5 to 80% by mass, and then removing unreacted isocyanate and purification. In this process, 1-6 valent alcohol compounds can be used in combination.

[0289] Examples of isocyanates containing biuret bonds include the biuret-modified 1,6-hexamethylene diisocyanate (HDI), the biuret-modified isophorone diisocyanate (IPDI), and the biuret-modified toluene diisocyanate (TDI), as shown below. Commercially available products include Desmodule N75, Desmodule N100, and Desmodule N3200 from Sumika Covestro Urethane Co., Ltd., and Duranate 24A-100, Duranate 22A-75P, and Duranate 21S-75E from Asahi Kasei Corporation.

[0290] [ka]

[0291] Isocyanates containing isocyanurate bonds are obtained, for example, by carrying out an isocyanuration reaction using a catalyst, stopping the reaction when the conversion rate reaches approximately 5 to 80% by mass, and then removing and purifying the unreacted isocyanate. In this process, 1-6 valent alcohol compounds can be used in combination.

[0292] As a catalyst for the above isocyanurate reaction, a catalyst that is generally basic is preferred. Examples of the catalysts mentioned above include: (1) Hydroxides of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, and trimethylbenzylammonium, and organic weak salts such as acetic acid and capric acid, (2) Hydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium, and organic weak salts such as acetic acid and capric acid, (3) Metal salts of alkylcarboxylic acids, such as tin, zinc, lead, (4) Metal alkoxides such as sodium and potassium, (5) Aminosilyl group-containing compounds such as hexamethyldisilazane, (6) Mannich bases, (7) Combined use of tertiary amines and epoxy compounds, (8) Phosphorus compounds such as tributylphosphine Examples include the following, and two or more types may be used in combination.

[0293] If the catalyst may adversely affect the properties of the paint or coating film, the catalyst may be neutralized with an acidic compound. Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid; sulfonic acids or their derivatives such as methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonate methyl ester, and p-toluenesulfonate ethyl ester; ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethyl glycol acid phosphate, butyl pyrophosphate, and butyl phosphate, and two or more may be used in combination.

[0294] Isocyanates having isocyanurate bonds include, for example, isocyanurate modified forms of HDI, IPDI, and TDI, as shown below. Commercially available products include Sumijoul N3300, Desmodule 3900, Desmodule Z4470BA, Desmodule XP2763, Desmodule IL1351BA, and Desmodule HLBA from Sumika Covestro Urethane Co., Ltd., and Duranate TPA-100, Duranate MFA-75B, Duranate TUL-100, and Duranate TSA-100 from Asahi Kasei Corporation.

[0295] [ka]

[0296] Isocyanates containing urethane bonds can be obtained, for example, by reacting a diisocyanate with a divalent to hexavalent alcohol compound such as trimethylolpropane (hereinafter referred to as TMP) in a molar ratio of hydroxyl groups of the alcohol compound to isocyanate groups of the isocyanate compound of approximately 1 / 2 to approximately 1 / 100, and then removing and purifying the unreacted isocyanate. Removal and purification of unreacted isocyanates is not always necessary.

[0297] Examples of isocyanates having urethane bonds include the reaction products of HDI and TMP, IPDI and TMP, and TDI and TMP, as shown below. Commercially available products include Sumijoule HT, Desmodule L75(C), Desmodule UltraL75, and Desmodule L67BA from Sumika Covestro Urethane Co., Ltd., and Duranate P301-75E, Duranate AE700-100, Duranate E402-80B, and Duranate E405-70B from Asahi Kasei Corporation.

[0298] [ka]

[0299] Known blocking agents for isocyanates in which a portion of the isocyanate groups of the above-mentioned isocyanates or the modified isocyanates are encapsulated with known blocking agents include, for example, phenols such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and dieth Examples include alcohols such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; pyrazoles such as 3,5-dimethylpyrazole and 1,2-pyrazole; triazoles such as 1,2,4-triazole; halogen-substituted alcohols such as ethylene chlorhydrin and 1,3-dichloro-2-propanol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propyllactam; and active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate. Other examples include amines, imides, mercaptans, imines, ureas, diaryls, and the like.

[0300] Examples of blocking agents include alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds. Alcohol compounds, lactam compounds, oxime compounds, and pyrazole compounds are preferred, and when combined with an onium salt represented by formula (1), the blocking agent can be dissociated in a short time even at low temperatures of less than 100°C. Therefore, alcohol compounds are preferred, and fluorinated alcohol compounds are particularly preferred.

[0301] Examples of alcohol compounds include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol. Alcohol compounds also include fluorinated alcohol compounds such as 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol. The alcohol compound is preferably a fluorinated alcohol compound, and particularly preferably 2,2,2-trifluoroethanol.

[0302] Examples of phenolic compounds include phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol 2-hydroxypyridine.

[0303] Examples of amine compounds include diisopropylamine.

[0304] Examples of lactam compounds include ε-caprolactam, δ-valerolactam, and γ-butyrolactam, with ε-caprolactam being preferred.

[0305] Specific examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, and methyl isobutyl ketoxime, with methyl ethyl ketoxime being preferred.

[0306] Examples of pyrazole compounds include 1,2-pyrazole and 3,5-dimethylpyrazole, and examples of triazole compounds include 1,2,4-triazole, with 3,5-dimethylpyrazole being preferred.

[0307] Examples of active methylene compounds include methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate.

[0308] In the blocked isocyanate composition of the present invention, known catalysts, additives, pigments, solvents, etc., commonly used in the art for polyurethane production may be used as needed.

[0309] The known catalysts for polyurethane production are not particularly limited, and include, for example, tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octoate, tin laurate, bismuth compounds such as bismuth octoate, bismuth naphthenate, bismuth acetylacetonate, tetra-n-butyl titanate, tetraisopropyl titanate, Titanium compounds such as titanium terephthalate, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,4-diazabicyclo[2.2.2]octane(D Examples include tertiary amine compounds such as ABCO), 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; and quaternary ammonium organic acid salts such as tetramethylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium forate, and 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

[0310] The additives are not particularly limited, but include, for example, UV absorbers such as hindered amines, benzotriazoles, and benzophenones; color inhibitors such as perchlorates and hydroxylamines; antioxidants such as hindered phenols, phosphorus, sulfur, and hydrazides; urethane catalysts such as tin, zinc, and amines; and other leveling agents, rheology control agents, and pigment dispersants.

[0311] The pigments are not particularly limited and include, for example, organic pigments such as quinacridone, azo, and phthalocyanine pigments; inorganic pigments such as titanium dioxide, barium sulfate, calcium carbonate, and silica; and other pigments such as carbon-based pigments, metallic foil pigments, and rust-preventive pigments.

[0312] The solvents are not particularly limited and include, for example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin; and water. These solvents may be used individually or in combination of two or more.

[0313] The thermosetting resin composition of the present invention will now be described.

[0314] The thermosetting resin composition of the present invention comprises the blocked isocyanate composition of the present invention and a compound having an isocyanate-reactive group.

[0315] Compounds having isocyanate-reactive groups include compounds having two or more active hydrogen groups, such as polyols, polyamines, and alkanolamines. These compounds having isocyanate-reactive groups may also be a mixture of two or more types.

[0316] In the present invention, a polyol is a compound having two or more hydroxyl groups. Examples include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and fluorine polyols. Among these, acrylic polyols are preferred as polyols from the viewpoint of weather resistance, chemical resistance, and hardness. Alternatively, polyester polyols are preferred as polyols from the viewpoint of mechanical strength and oil resistance. These polyols may also be mixtures of two or more types.

[0317] Examples of polyether polyols include aliphatic amine polyols, aromatic amine polyols, Mannich polyols, polyhydric alcohols, polyhydric phenols, bisphenols and other active hydrogen compounds, and compounds obtained by adding alkylene oxides to these. These polyether polyols may also be mixtures of two or more types.

[0318] Examples of aliphatic amine polyols include alkylenediamine polyols and alkanolamine polyols. These polyol compounds are polyfunctional polyol compounds with terminal hydroxyl groups obtained by ring-opening addition of at least one cyclic ether such as ethylene oxide or propylene oxide to an alkylenediamine or alkanolamine as an initiator. Known compounds can be used without limitation as alkylenediamines. Specifically, alkylenediamines with 2 to 8 carbon atoms, such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine, are preferred. These aliphatic amine polyols may also be mixtures of two or more types.

[0319] Aromatic amine polyols are polyfunctional polyether polyol compounds with terminal hydroxyl groups obtained by ring-opening and adding at least one cyclic ether such as ethylene oxide or propylene oxide to an aromatic diamine as an initiator. Any known aromatic diamine can be used as an initiator without limitation. Specifically, examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, and naphthalenediamine. Among these, the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine, or a mixture thereof) is particularly preferred. These aromatic amine polyols may also be mixtures of two or more types.

[0320] Mannich polyols are active hydrogen compounds obtained by the Mannich reaction of phenol and / or its alkyl-substituted derivatives, formaldehyde and alkanolamines, or polyol compounds obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide or propylene oxide. These Mannich polyols may also be mixtures of two or more types.

[0321] Examples of polyhydric alcohols include dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, etc.) and trihydric or higher alcohols (e.g., glycerin, trimethylolpropane, pentaerythritol, methyl glucoside, sorbitol, sucrose, etc.). These polyhydric alcohols may also be mixtures of two or more types.

[0322] Examples of polyhydric phenols include pyrogallol and hydroquinone. These polyhydric phenols may also be a mixture of two or more types.

[0323] Examples of bisphenols include bisphenol A, bisphenol S, bisphenol F, and low-level condensates of phenol and formaldehyde. These bisphenols may also be mixtures of two or more types.

[0324] Polyester polyols can be obtained, for example, by condensing a dibasic acid (either alone or a mixture of two or more) with a polyhydric alcohol (either alone or a mixture of two or more).

[0325] Examples of the aforementioned dibasic acids include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and carboxylic acids such as 1,4-cyclohexanedicarboxylic acid.

[0326] Examples of the aforementioned polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, and ethoxylated trimethylolpropane.

[0327] A specific method for producing polyester polyols is, for example, to mix the above components and heat them at approximately 160-220°C to carry out a condensation reaction. Alternatively, polycaprolactones, such as those obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyhydric alcohol, can also be used as polyester polyols.

[0328] These polyester polyols can be modified using aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and isocyanates obtained therefrom. In particular, from the viewpoint of weather resistance and resistance to yellowing, it is preferable to modify polyester polyols using aliphatic diisocyanates, alicyclic diisocyanates, and isocyanates obtained therefrom.

[0329] When the thermosetting resin composition of this embodiment is used as a water-based paint, some carboxylic acids derived from dibasic acids, etc., in the polyester polyol are left in place and neutralized with a base such as an amine or ammonia, thereby making the polyester polyol a water-soluble or water-dispersible resin.

[0330] Polyether polyols can be obtained, for example, by any of the following methods (1) to (3). (1) A method for obtaining polyether polyols by randomly or block adding an alkylene oxide alone or a mixture of polyvalent hydroxy compounds alone or a mixture of polyvalent hydroxy compounds using a catalyst.

[0331] Examples of the catalysts include hydroxides (lithium, sodium, potassium, etc.), strongly basic catalysts (alkoxides, alkylamines, etc.), and complex metal cyanide compounds (metallic porphyrins, zinc hexacyanocobaltate complexes, etc.).

[0332] Examples of the alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.

[0333] (2) A method for obtaining polyether polyols by reacting a polyamine compound with an alkylene oxide.

[0334] Examples of the polyamine compounds include ethylenediamines.

[0335] Examples of the alkylene oxide mentioned above include those similar to those exemplified in (1).

[0336] (3) A method for obtaining so-called polymer polyols by polymerizing acrylamide or the like using polyether polyols obtained in (1) or (2) as a medium.

[0337] Examples of the aforementioned polyvalent hydroxy compounds include the following (i) to (vi):

[0338] (i) Diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.

[0339] (ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol.

[0340] (iii) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and ribodesose.

[0341] (iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, genthiobiose, lactose, and melibiose.

[0342] (v) Trisaccharides such as raffinose, gentianose, and meletitose.

[0343] (vi) Tetrasaccharides such as stachyose.

[0344] Acrylic polyols can be obtained, for example, by polymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule, or by copolymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule with, if necessary, another monomer copolymerizable with the polymerizable monomer.

[0345] Examples of polymerizable monomers having one or more active hydrogen atoms in a single molecule include (i) to (vi) below. These may be used individually or in combination of two or more types.

[0346] (i) Acrylic acid esters having active hydrogen, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate. (ii) Methacrylic acid esters having active hydrogen, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

[0347] (iii) (meth)acrylic acid esters having polyvalent active hydrogen, such as (meth)acrylic acid monoesters of triols like glycerin and trimethylolpropane.

[0348] (iv) Monoethers of polyether polyols (e.g., polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) and (meth)acrylic acid esters having the above-mentioned active hydrogen.

[0349] (v) Adducts of glycidyl (meth)acrylate with monobasic acids (e.g., acetic acid, propionic acid, p-tert-butylbenzoic acid, etc.).

[0350] (vi) Adducts obtained by ring-opening polymerization of lactones (e.g., ε-caprolactam, γ-valerolactone, etc.) to the active hydrogen of the above-mentioned (meth)acrylic acid esters having active hydrogen.

[0351] Other monomers copolymerizable with the polymerizable monomer include, for example, (i) to (iv) below. These may be used individually or in combination of two or more.

[0352] (i) (meth)acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, and glycidyl methacrylate.

[0353] (ii) Unsaturated amides such as acrylic acid, methacrylic acid, maleic acid, itaconic acid (unsaturated carboxylic acids such as acrylamide, N-methylolacrylamide, and diacetoneacrylamide).

[0354] (iii) Vinyl monomers having a hydrolyzable silyl group, such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acrylopropyltrimethoxysilane.

[0355] (iv) Other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0356] Specific methods for producing acrylic polyols include, for example, a method in which the above-mentioned monomer components are solution polymerized in the presence of known radical polymerization initiators such as peroxides and azo compounds, and then diluted with an organic solvent as necessary to obtain an acrylic polyol.

[0357] When the thermosetting resin composition of this embodiment is used as a water-based coating, a water-based acrylic polyol can be produced by using known methods such as solution polymerization of the above monomer components to convert them into an aqueous layer, or emulsion polymerization. In this case, the acidic portion, such as carboxylic acid-containing monomers like acrylic acid and methacrylic acid, or sulfonic acid-containing monomers, can be neutralized with amines or ammonia to impart water-soluble or water-dispersible properties to the acrylic polyol.

[0358] Examples of polyolefin polyols include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, and hydrogenated polyisoprene having two or more hydroxyl groups.

[0359] Furthermore, in polyolefin polyols, the number of hydroxyl groups is preferably three, as this allows for higher coating film strength.

[0360] In this specification, "fluorinated polyol" means a polyol containing fluorine in its molecule. Specific examples of fluorinated polyols include copolymers of fluoroolefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, and vinyl monocarboxylate esters, as disclosed in Japanese Patent Publication No. 57-34107 and Japanese Patent Publication No. 61-275311, among others.

[0361] The lower limit of the hydroxyl value of the polyol is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, and even more preferably 30 mg KOH / g or more.

[0362] On the other hand, there are no specific limitations on the upper limit of the hydroxyl value of polyols; for example, it is sufficient if it is 200 mg KOH / g or less.

[0363] In other words, the hydroxyl value of the polyol is preferably 10 mg KOH / g or more and 200 mg KOH / g or less, more preferably 20 mg KOH / g or more and 200 mg KOH / g or less, and even more preferably 30 mg KOH / g or more and 200 mg KOH / g or less.

[0364] Furthermore, the acid value of the polyol is preferably 0 mg KOH / g or more and 30 mg KOH / g or less.

[0365] The hydroxyl value and acid value can be measured in accordance with JIS K1557.

[0366] The molar equivalent ratio (NCO / OH) of the isocyanate groups of the above-described blocked isocyanate composition to the hydroxyl groups of the polyol is preferably 0.2 or more and 5.0 or less, more preferably 0.4 or more and 3.0 or less, and even more preferably 0.5 or more and 2.0 or less.

[0367] The polyamine used has two or more primary or secondary amino groups in one molecule, and among these, those having three or more are preferred.

[0368] Specific examples of polyamines include diamines such as ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, and isophoronediamine; chain polyamines having three or more amino groups such as bishexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, and tetrapropylenepentamine; and cyclic polyamines such as 1,4,7,10,13,16-hexazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane.

[0369] The term "alkanolamine" refers to a compound having an amino group and a hydroxyl group in one molecule. Examples of alkanolamines include monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono-, di-(n- or iso-)propanolamine, ethylene glycol-bis-propylamine, neopentanolamine, and methylethanolamine.

[0370] The thermosetting resin composition of this embodiment may optionally contain a melamine-based curing agent such as a fully alkyl type, methylol type, or alkylamino group type alkyl.

[0371] The thermosetting resin composition of this embodiment may contain an organic solvent.

[0372] Furthermore, the compound having the isocyanate-reactive group and the blocked isocyanate composition described above may contain an organic solvent.

[0373] The organic solvent is preferably one that is compatible with the above-mentioned blocked isocyanate composition.

[0374] Examples of organic solvents include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin; and water. These solvents may be used individually or in combination of two or more.

[0375] Furthermore, the thermosetting resin composition of this embodiment can be used as an aqueous thermosetting resin composition dissolved or dispersed in water. When the thermosetting resin composition of the present invention is used as an aqueous thermosetting resin composition, surfactants or solvents that tend to be miscible with water may be used with respect to the blocked isocyanate composition of the present invention in order to improve the compatibility of the thermosetting resin composition. Examples of surfactants include anionic surfactants such as aliphatic soaps, rosinate soaps, alkyl sulfonates, dialkylaryl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkylaryl sulfates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene oxypropylene block copolymers. Solvents that tend to be miscible with water include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butyl glycol, N-methylpyrrolidone, butyl diglycol, or butyl diglycol acetate.

[0376] Among the above solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butyl glycol, N-methylpyrrolidone, and butyl diglycol are preferred, and diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether are more preferred. These solvents may be used individually or in combination of two or more. Furthermore, ester solvents such as ethyl acetate, n-butyl acetate, and cellosolve acetate are undesirable because the solvents themselves may undergo hydrolysis during storage.

[0377] In the thermosetting resin composition of the present invention, the blending ratio of the blocked isocyanate composition and the compound having an isocyanate-reactive group is determined by the required physical properties and is not particularly limited. Typically, the ratio of [amount of active isocyanate groups of the blocked isocyanate compound in the blocked isocyanate composition (mol)] / [amount of active hydrogen groups of the compound having an isocyanate-reactive group (mol)] is in the range of 0.2 to 5, and preferably in the range of 0.5 to 3. The effective isocyanate group of the blocked isocyanate compound refers to the isocyanate group that is regenerated when the blocking agent is dissociated from the blocked isocyanate compound.

[0378] In the thermosetting resin composition of the present invention, known catalysts, additives, pigments, etc. commonly used in the art for the production of polyurethane may be used as needed, and may also be used in combination with known blocked isocyanates.

[0379] The known catalysts for polyurethane production are not particularly limited, and include, for example, tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octoate, tin laurate, bismuth compounds such as bismuth octoate, bismuth naphthenate, bismuth acetylacetonate, tetra-n-butyl titanate, tetraisopropyl titanate, Titanium compounds such as titanium terephthalate, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,4-diazabicyclo[2.2.2]octane(D Examples include tertiary amine compounds such as ABCO), 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; and quaternary ammonium organic acid salts such as tetramethylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium forate, and 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

[0380] The additives are not particularly limited and include, for example, UV absorbers such as hindered amines, benzotriazoles, and benzophenones; color inhibitors such as perchlorates and hydroxylamines; antioxidants such as hindered phenols, phosphorus, sulfur, and hydrazides; urethane catalysts such as tin, zinc, and amines; and various other additives used in the relevant field, such as leveling agents, defoamers, rheology control agents, thixotropy imparters / thickeners, light stabilizers, plasticizers, surfactants, coupling agents, flame retardants, rust inhibitors, fluorescent whitening agents, and pigment dispersants.

[0381] The pigments are not particularly limited and include, for example, organic pigments such as quinacridone, azo, and phthalocyanine pigments; inorganic pigments such as titanium dioxide, barium sulfate, calcium carbonate, and silica; and other pigments such as carbon-based pigments, metallic foil pigments, and rust-preventive pigments.

[0382] Known blocked isocyanates include, for example, blocked isocyanates obtained by reacting an isocyanate with a known blocking agent. Known blocking agents include, for example, phenol compounds such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oxime compounds such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether. Examples include alcohol compounds such as benzyl alcohol, pyrazole compounds such as 3,5-dimethylpyrazole and 1,2-pyrazole, triazole compounds such as 1,2,4-triazole, halogen-substituted alcohol compounds such as ethylene chlorhydrin and 1,3-dichloro-2-propanol, lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propyllactam, and active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate. Other examples include amine compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds.

[0383] The thermosetting resin composition of the present invention can be used in paints for automobiles, buildings, metal products such as steel furniture, woodworking products such as musical instruments, machinery and vehicles such as construction equipment, building materials such as window frames, electrical appliances such as office equipment, coatings for artificial leather and rubber rolls, inks, adhesives, sealants for electronic components, sealing materials for automobiles and buildings, molding materials for 3D printers, and the like.

[0384] Next, a method for curing the thermosetting resin composition of the present invention will be described.

[0385] In the method of the present invention, a thermosetting resin composition which is a mixture of the above-mentioned blocked isocyanate composition and a compound having an isocyanate-reactive group is heated.

[0386] The reaction temperature varies depending on the blocked isocyanate compound and onium salt (1) in the blocked isocyanate composition used, but can be approximately 60 to 250°C, preferably 80 to 200°C. The reaction time can be approximately 30 seconds to 5 hours, preferably 1 minute to 60 minutes.

[0387] The cured product of the present invention can be produced by following the curing method for the thermosetting resin composition of the present invention described above. [Examples]

[0388] The present invention will be described in more detail using manufacturing examples and embodiments, but the present invention is not limited to these embodiments. (1) Infrared spectroscopy (IR analysis) conditions Equipment: FT-IR-6600 manufactured by JASCO Corporation Measurement method: Total internal reflection (crystal: germanium) Total number of times: 16 (2) 1 H-NMR analysis conditions Equipment: Bruker AV400 Frequency: 400MHz (3) Curing temperature and time measurement conditions Equipment: Madoka Automatic Curing Time Measurement Device manufactured by Cyber ​​Co., Ltd. Stirring rod: Model number 3JC-5060W Stirring speed: rotation 100 rpm, revolution 25 rpm (4) Method for calculating solid content Approximately 1.5 g of the sample was heated at 110°C for 3 hours, and the solid content (%) of the sample was calculated from the mass before and after heating. (5) Composition of thermosetting resin composition Blocked isocyanate compounds, compounds containing isocyanate-reactive groups, and amidate compounds were added so that the ratio of effective NCO groups (mol): hydroxyl groups (mol): amidate groups (mol) was 1.00:0.95:0.05. Methyl isobutyl ketone was then added so that the ratio of solids (g) of the blocked isocyanate compound to solvent (g) was 1.0:1.0. Note that the solvent here includes the solvent used to dilute the blocked isocyanate compound. The effective NCO groups (mol) and hydroxyl groups (mol) were calculated using the following formula.

[0389] Effective NCO groups (mol) = Amount of blocked isocyanate charged (g) ÷ Effective NCO group content of blocked isocyanate (%) ÷ 4.202 Hydroxyl groups (mol) = Amount of polyol added (g) × Hydroxyl value of polyol (mgKOH / g) ÷ 56.1

[0390] [Production Example 1] Synthesis of 1,3-di-tert-butylimidazolium bicarbonate ([tBuI][C])

[0391] [ka]

[0392] In a nitrogen-purged 1 L cylindrical flask, 40% glyoxal (299.98 g, 2.065 mol), 40% formaldehyde aqueous solution (151.71 g, 2.20 mol), and acetic acid (154.30 g, 2.569 mol) were mixed. This mixture was heated to 50°C, and tert-butylamine (250.39 g, 3.422 mol) was added dropwise over 1 hour. The mixture after addition was stirred at 50°C for 3 hours and then cooled to 25°C. The cooled reaction mixture was concentrated under reduced pressure at 60°C for 1 hour. Dimethyl carbonate (313.03 g, 3.474 mol) was added to the concentration residue and stirred under reflux for 24 hours. After stirring, the reaction mixture was cooled to 25°C and then concentrated under reduced pressure at 60°C for 1 hour. Water (400 g) was added to this concentration residue and stirred at 25°C for 1 hour. The reaction mixture was cooled to 25°C after stirring, and then concentrated under reduced pressure at 60°C for 1 hour. Acetone (500g) was added to the concentrated residue, and the mixture was stirred at 25°C for 1 hour, followed by filtration. The filtered residue was dried under reduced pressure at 60°C for 1 hour to obtain 100g (24.1%) of [tBuI][C]. 1 H-NMR(CDCl3)δ(ppm)=7.35(s,2H),1.75(s,18H)

[0393] [Production Example 2] Synthesis of (2-methoxyethyl)diethylmethylammonium methylcarbonate

[0394] [ka]

[0395] In a nitrogen-purged 5 L autoclave, methoxyethyldiethylamine (1100 g, 8.38 mol), dimethyl carbonate (1512.3 g, 16.79 mol), and methanol (274.8 g) were added. The mixture was stirred at 130°C for 26 hours. 2732.5 g of the reaction solution was obtained as a methanol solution of (2-methoxyethyl)diethylmethylammonium methyl carbonate.

[0396] [Production Example 3] Synthesis of tri-n-butyl-n-hexylphosphonium bicarbonate

[0397] [ka]

[0398] Tri-n-butyl-n-hexylphosphonium bromide (1.00 g, 2.72 mmol) and potassium bicarbonate (3.02 g, 30.1 mmol) were added to a nitrogen-purged 100 ml cylindrical flask. Dichloromethane (5 g) was then added, and the mixture was stirred at 25°C for 10 hours. The resulting suspension was filtered at 25°C. The filtrate was concentrated under reduced pressure at 60°C to obtain 530 mg of tri-n-butyl-n-hexylphosphonium bicarbonate (yield 55.9%). 1 H-NMR(CD2Cl3)δ(ppm)=2.36-2.26(m,8H), 1.49-1.35(m,16H), 1.24-1.20(m,4H), 0.86(t,J=7.2Hz,9H), 0.79(t,J=7.2Hz, 3H)

[0399] [Production Example 4] Synthesis of N-Hexadecylpyridinium Bicarbonate

[0400] [ka]

[0401] N-hexadecylpyridinium bromide (1.00 g, 2.60 mmol) and potassium bicarbonate (3.00 g, 29.9 mmol) were added to a nitrogen-purged 100 ml cylindrical flask. Dichloromethane (5 g) was then added, and the mixture was stirred at 25°C for 10 hours. The resulting suspension was filtered at 25°C. The filtrate was concentrated under reduced pressure at 60°C to obtain 1.12 g (yield quant.) of N-hexadecylpyridinium bicarbonate. 1 H-NMR(CD2Cl3)δ(ppm)=9.54(dd,J=1.2, 6.8Hz,2H), 8.54(tt,J=1.2,6.8Hz,1H), 8.13(dd,6.8, 7.6Hz,2H), 4.95(t,J=7.6Hz,2H), 1.99(t,J=7.6, 2H)1.33-1.18(m,26H)0.81(t,J=6.8Hz,3H)

[0402] [Production Example 5] Synthesis of Methyl-N-Phenylcarbamate

[0403] [ka]

[0404] Methanol (25.7 g, 802 mmol) and triethylamine (100 mg, 0.98 mmol) were added to a nitrogen-purged 100 ml cylindrical flask. The mixture was heated to 50°C, phenyl isocyanate was added dropwise, and the mixture was aged at 50°C for 5 hours. The resulting reaction mixture was concentrated under reduced pressure at 60°C to obtain 25.18 g of methyl-N-phenylcarbamate (yield 97.2%). 1 H-NMR(CD2Cl3)δ(ppm)=7.39(d, J=7.6Hz,2H), 7.30(t,J=8.4Hz,2H)7.06(tt,J=1.2,7.2Hz,1H), 3.74(s,3H)

[0405] [Production Example 6] Synthesis of 2,2,2-trifluoroethyl-Nn-hexylcarbamate

[0406] [ka]

[0407] 2,2,2-trifluoroethanol (20.13 g, 200 mmol), toluene (20 g), and triethylamine (196 mg, 1.93 mmol) were added to a nitrogen-purged 100 ml cylindrical flask. The mixture was heated to 50°C, and n-hexyl isocyanate was added dropwise. The mixture was aged at 50°C for 5 hours. The resulting reaction solution was concentrated under reduced pressure at 60°C to obtain 24.70 g of 2,2,2-trifluoroethyl-Nn-hexylcarbamate (yield 86.9%). 1H-NMR(CD2Cl3)δ(ppm)=4.46(q,J=8.8Hz,2H), 4.46(q,J=7.2Hz,2H), 1.50(t, J=7.2Hz,2H), 1.35-1.29(m,6H), 0.89(t, J=6.8Hz,3H)

[0408] [Production Example 7] Method for producing methyl-N-2-ethylhexylcarbamate [MN2EHC]

[0409] [ka]

[0410] In a nitrogen-purged 200 ml cylindrical flask, dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) (38.1 g, 424 mmol) was dissolved with 2-ethylhexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (50 g, 386 mmol) and potassium tert butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) (433 mg, 3.86 mmol). The resulting solution was stirred at 60°C for 6 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain 53.0 g (yield 73.4%) of [MN2EHC] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=3.62(s,3H), 3.06(t,J=6.0Hz,2H),1.40-1.23(m,9H), 0.92-0.85(m,6H)

[0411] [Manufacturing Example 8] Method for producing toluenedimethylcarbamate ([TDMC])

[0412] [ka]

[0413] Methanol (45.7 g) and triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (5.80 mg, 0.574 mmol) were added to a nitrogen-purged 180 ml cylindrical flask. The temperature was raised to 60°C, and toluene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.0 g, 57.4 mmol) was added dropwise at 60-65°C. The resulting solution was stirred and reacted at 60°C for 2 hours. The resulting reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 13.1 g (yield quantity) of [TDMC] represented by the above formula. It is presumed to be a mixture of compounds represented by the above formula. 1 Figure 1 shows the results of the 1H-NMR (DMSO-d6) analysis, and Figure 2 shows the results of the IR analysis.

[0414] [Manufacturing Example 9] Method for producing triethylmethylammonium methyl carbonate ([TEMA][MC])

[0415] [ka]

[0416] Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (100 g, 988 mmol) and dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) (150 g, 1.66 mol) were added to a 180 ml autoclave purged with nitrogen. This mixture was stirred at 125°C for 12 hours and then cooled to 25°C. The cooled reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 121 g of [TEMA][MC] represented by the above formula (yield 64%). 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=3.44(q,J=6.8,6H),3.37(s,3H),1.32(t,J=6.80,9H)

[0417] [Production Example A-1] Synthesis of 1,3-di-tert-butylimidazolium methyl-N-phenylcarbamate ([DtBI][MNPhC])

[0418] [ka]

[0419] In a nitrogen-purged 200 ml cylindrical flask, di-tert-butylimidazolium bicarbonate (7.28 g, 30.45 mmol) obtained in Preparation Example 1 and methyl-N-phenylcarbamate (4.619 g, 30.56 mmol) obtained in Preparation Example 5 were added, and toluene (10 g) was added to suspend the mixture. The resulting suspension was stirred and reacted at 25°C for 1 hour. The resulting reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 10.62 g (yield quant.) of [DtBI][MNPhC] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(MeOD-d4)δ(ppm)=7.87(s,2H), 7.41(d,J=8.0Hz,2H), 7.26(t,J=8.4Hz,2H), 7.00(t,J=7.2Hz,1H), 3.73(s,3H), 1.69(s,18H)

[0420] [Production Example A-2] Synthesis of 1,3-di-tert-butylimidazolium 2,2,2-trifluoroethyl-Nn-hexylcarbamate ([DtBI][TFENPhC])

[0421] [ka]

[0422] In a nitrogen-purged 100 ml cylindrical flask, di-tert-butylimidazolium bicarbonate (1.00 g, 4.40 mmol) obtained in Preparation Example 1 and 2,2,2-trifluoroethyl-Nn-hexylcarbamate (1.06 g, 4.40 mmol) obtained in Preparation Example 6 were added, and toluene (10 g) was added to suspend the mixture. The resulting suspension was stirred and reacted at 25°C for 1 hour. The resulting reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 1.95 g (yield quant.) of [DtBI][TFENPhC] represented by the above formula. 1The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=10.35(s, 1H), 7.56(s,2H), 3.81(q,J=9.6Hz,2H), 2.98(q,J=6.4Hz,2H), 1.67(s,18H), 1.38-1.35(m,2H),1.28-1.24(m,6H), 0.84(t,J=6.0Hz,3H)

[0423] [Production Example A-3] Synthesis of 1,3-di-tert-butylimidazolium N-phenylacetamidate ([DtBI][AcA])

[0424] [ka]

[0425] Di-tert-butylimidazolium bicarbonate (5.00 g, 20.63 mmol) and acetanilide (3.11 g, 23.03 mmol) obtained in Preparation Example 1 were added to a nitrogen-purged 100 ml cylindrical flask, and toluene (15 g) was added to suspend the mixture. The resulting suspension was stirred and reacted at 25°C for 6 hours. The resulting reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 7.69 g (yield quantity) of [DtBI][AcA] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=10.07(br,1H), 7.72(dd,J=8.8,1.2Hz,2H), 7.51(s,2H),7 .16(dd,J=8.4,7.6Hz,2H), 6.94(tt,J=7.2,1.2Hz,1H), 2.11(s,3H), 1.69(s,18H)

[0426] [Production Example A-4] Synthesis of 1,3-di-tert-butylimidazolium N,N'-dimethylurate ([DtBI][DMU])

[0427] [ka]

[0428] Di-tert-butylimidazolium bicarbonate (5.00 g, 20.63 mmol) and dimethylurea (1.81 g, 20.63 mmol) obtained in Preparation Example 1 were added to a nitrogen-purged 100 ml cylindrical flask, and toluene (15 g) was added to suspend the mixture. The resulting suspension was stirred and reacted at 25°C for 6 hours. The resulting reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 6.68 g (yield quant.) of [DtBI][DMU] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=9.98(br,1H),7.60(s,2H),6.90(br,1H),2.58(s,3H),2.57(s,3H),1.66(s,18H)

[0429] [Production Example A-5] Synthesis of (2-methoxyethyl)diethylmethylammonium methyl-N-phenylcarbamate ([DEME][MNPhC])

[0430] [ka]

[0431] In a nitrogen-purged 50 ml round-bottom flask, (2-methoxyethyl)diethylmethylammonium methyl carbonate (5.90 g, 25.0 mmol) obtained in Preparation Example 2 and methyl-N-phenylcarbamate (3.77 g, 25.0 mmol) obtained in Preparation Example 5 were added, and tetrahydrofuran (10 g) was added to suspend the mixture. The resulting suspension was stirred at 60°C for 3 hours to allow the reaction to proceed. After cooling the resulting reaction solution to 25°C, it was concentrated under reduced pressure at 60°C for 1 hour to obtain 6.98 g (yield 89.9%) of [DEME][MNPhC] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1H-NMR(CDCl3)δ(ppm)=7.46(d,J=7.6Hz,2H),7.20(t,J=7.6Hz,2H),6.94(t,J=7.6Hz,1H ), 3.68-3.66(m,5H),3.49-3.43(m,6H),3.25(s,3H),3.10(s,3H),1.23(t, J=7.2Hz,6H)

[0432] [Production Example A-6] Synthesis of tri-n-butyl-n-hexylphosphonium methyl-N-phenylcarbamate ([TBHP][MNPhC])

[0433] [ka]

[0434] In a nitrogen-purged 100 ml cylindrical flask, 3.00 g of tri-n-butyl-n-hexylphosphonium bicarbonate (8.60 mmol) obtained in Preparation Example 3 and 1.36 g of methyl-N-phenylcarbamate (9.03 mmol) obtained in Preparation Example 5 were added, and dichloromethane (9 g) was added to suspend the mixture. The resulting suspension was stirred at 25°C for 6 hours. After filtration of the suspension, the filtration residue was dried under reduced pressure at 60°C for 1 hour to obtain 3.44 g of [TBHP][MNPhC] represented by the above formula (yield 91.4%). 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=7.44(d,J=8.0Hz,2H),7.27(t,J=7.2Hz,2H),7.02(tt,7.6,1.2Hz,1H),3.76(s,3 H), 2.39-2.30(m,8H), 1.56-1.45(m,16H), 1.33-1.29(m,4H), 0.96(t,J=7.2Hz,9H), 0.89(t,J=6.8Hz,3H)

[0435] [Production Example A-7] Synthesis of N-Hexadecylpyridinium Methyl-N-Phenylcarbamate ([HdPy][MNPhC])

[0436] [ka]

[0437] In a nitrogen-purged 100 ml cylindrical flask, N-hexadecylpyridinium bicarbonate (3.00 g, 8.20 mmol) obtained in Preparation Example 4 and methyl-N-phenylcarbamate (1.30 g, 8.61 mmol) obtained in Preparation Example 5 were added, and dichloromethane (9 g) was added to suspend the mixture. The resulting suspension was stirred at 25°C for 6 hours. After filtration of the suspension, the filtration residue was dried under reduced pressure at 60°C for 1 hour to obtain 4.03 g of [HdPy][MNPhC] represented by the above formula (yield quant.). 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=9.41(dd,J=7.2,1.6Hz,2H),8.48(tt,J=8.0,1.2Hz,1H),8.09(t,J=6.8Hz,2H),7.45(d,J=8.0Hz,2H),7.28(t, J=7.6Hz,2H),7.03(tt,J=7.6,1.2Hz,1H),4.92(t,J=7.6Hz,2H),3.72(s,3H),2.02(m,2H),1.33-1.25(m,26H),0.872(t,J=7.2Hz,3H)

[0438] [Manufacturing Example A-8] Method for producing trimethyl-n-octylammonium dimethylurea ([TMOA][DMU])

[0439] [ka]

[0440] In a nitrogen-purged 200 ml cylindrical flask, 27.8 g (113 mol) of trimethyl-n-octylammonium methyl carbonate obtained in Comparative Production Example A-1 and 10.0 g (113 mmol) of dimethylurea (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and methanol (17.49 g) was added to dissolve them. The resulting solution was stirred under reflux for 5 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain 29.13 g (yield quant.) of [TMOA][DMU] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(CD2Cl2)δ(ppm)=3.38(t,J=4.0Hz, 2H), 3.25(s,9H),2.63(s,6H), 1.74-1.70(m,2H), 1.35-1.28(m,10H), 0.88(t,J=7.2Hz,3H)

[0441] [Manufacturing Example A-9] Method for producing trimethyl-n-octylammonium methyl-N-2-ethylhexylcarbamate ([TMOA][MN2EHC])

[0442] [ka]

[0443] In a nitrogen-purged 200 ml cylindrical flask, 26.1 g (10⁶ mol) of trimethyl-n-octylammonium methyl carbonate obtained in Comparative Production Example A-1 and 20.0 g (10⁶ mmol) of [MN₂EHC] obtained in Production Example 7 were added, and methanol (92 g) was added to dissolve them. The resulting solution was stirred under reflux for 6 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain 42.15 g (yield quant.) of [TMOA][MN₂EHC] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1H-NMR(CD2Cl2)δ(ppm)=3.60(s,3H),3.43(t,J=7.2Hz,2H),3.30(s,9H),3. 06(t,J=4.0Hz,2H),1.73-1.69(m,2H),1.39-1.24(m,19H)0.90-0.85(m,9H)

[0444] [Manufacturing Example A-10] Method for producing trimethyl-n-octylammonium toluenedimethylcarbamate ([TMOA][TDMC])

[0445] [ka]

[0446] In a nitrogen-purged 200 ml cylindrical flask, 5.14 g of trimethyl-n-octylammonium methyl carbonate obtained in Comparative Production Example A-1 and 5.00 g of toluenebis(methylcarbamate) obtained in Production Example 8 were added, and THF (15 g) was added to dissolve them. The resulting solution was stirred under reflux for 3 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain 9.94 g (yield quant.) of a mixture of the compounds represented by the above formula ([TMOA][TDMC]). 1 The results of the 1H-NMR (DMSO-d6) analysis are shown in Figure 3, and the results of the IR analysis are shown in Figure 4.

[0447] [Manufacturing Example A-11] Method for producing trimethyl-n-octylammonium methyl-N-phenylcarbamate ([TMOA][MNPhC])

[0448] [ka]

[0449] In a nitrogen-purged 200 ml cylindrical flask, trimethyl-n-octylammonium methyl carbonate (3 g, 12.1 mol) obtained in Comparative Preparation Example A-1 and methyl-N-phenylcarbamate (1.82 g, 12.1 mmol) obtained in Preparation Example 5 were added, and THF (5 g) was added to dissolve them. The resulting solution was stirred under reflux for 4 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C for 1 hour to obtain 4.23 g (yield quant.) of [TMOA][MNPhC] represented by the above formula. 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(DMSO-d6)δ(ppm)=7.45(dd,J=8.4,0.8Hz,2H),7.26(t,J=7.6Hz,2H),6.97(tt,J=7.2,0.8Hz,1H),3. 65(s,3H),3.37(t,J=4.0Hz,2H),3.04(s,9H),16.7-1.643(m,2H),1.29-1.28(m,10H),0.87(t,J=7.2Hz,3H)

[0450] [Manufacturing Example A-12] Method for producing trimethyl-n-octylammonium methyl-N-phenylcarbamate ([TMOA][MNPhC])

[0451] [ka]

[0452] [TMOA][MC] (10 g, 52.2 mmol) obtained in Preparation Example 9 and methyl-N-phenylcarbamate (7.89 g, 52.2 mmol) obtained in Preparation Example 5 were added to a 100 ml autoclave purged with nitrogen, and THF (20 g) was added to dissolve them. This mixture was stirred under reflux conditions for 3 hours and then cooled to 25°C. The cooled reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 16.3 g of [TEMA][MNPhC] represented by the above formula (yield quant.). 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR (DMSO-d6)δ (ppm) =1 H-NMR(DMSO-d6)δ(ppm)=7.42(dd,J=8.8,1.2Hz,2H),7.18(t,J=7.6Hz,2H),6.85(tt,J=7.6, 1.2Hz,1H),3.58(s,3H),3.24(q,J=7.6Hz,6H),2.88(s,3H),1.18(t,J=7.2Hz,9H)

[0453] [Comparative Manufacturing Example A-1] Method for producing trimethyl-n-octylammonium methyl carbonate ([TMOA][MC])

[0454] [ka]

[0455] Dimethyl-n-octylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (10.00 g, 63.5 mmol) and dimethyl carbonate (17.1 g, 190 mmol) were added to a 100 ml autoclave purged with nitrogen. This mixture was stirred at 120°C for 12 hours and then cooled to 25°C. The cooled reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain 16.2 g of [TMOA][MC] represented by the above formula (yield quant.). 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(DMSO-d6)δ(ppm)=3.27(t,J=8.4Hz,2H),3.16(s,3H),3.04(br,9H),1.66(br,2H )1.27(br,10H),0.87(t,J=6.8Hz,3H)

[0456] [Production Example B-1] Synthesis of 2,2,2-trifluoroethanol block of biuret-type HDI In a nitrogen-purged 200 mL three-neck reactor, 150.0 g of biuret-type HDI (Desmodule N3200A, NCO group content: 22.8 (%), manufactured by Sumika Covestro Urethane Co., Ltd.) (NCO group: 0.81 mol) and 73.3 g of methyl isobutyl ketone (hereinafter referred to as MIBK) were charged, and the temperature was raised to 65°C. Then, 1.4 g of triethylamine (hereinafter referred to as TEA) was added. Subsequently, 27.0 g (0.99 mol) of 2,2,2-trifluoroethanol (hereinafter referred to as TFE) and 79.4 g of MIBK were added dropwise to the reaction vessel, and the mixture was stirred at 65°C for 2 hours. Infrared spectroscopy analysis revealed that the isocyanate group was at 2270 cm⁻¹. -1 The disappearance of the infrared absorption peak in the vicinity was confirmed. The obtained reaction solution was concentrated under reduced pressure, and after removing the TEA and most of the MIBK, 59.9 g of MIBK was added to obtain 306.1 g of MIBK solution of biuret-type HDI TFE block bodies. The solid content of the obtained biuret-type HDI TFE block bodies was 76.1%, and the effective NCO group content was 11.2%.

[0457] [Example 1] A thermosetting resin composition was prepared by adding the TFE block of biuret-type HDI obtained in Production Example B-1, polyester polyol (P-510, manufactured by Kuraray Co., Ltd.), and the blocking agent dissociation catalyst [DtBI] [MNPhC] prepared in Production Example A-1, and stirring for 30 minutes, so that the composition of the thermosetting resin composition was effective NCO groups (mol):hydroxyl groups (mol):curing catalyst (mol) = 1.00:0.95:0.05. Approximately 0.6 mL of the prepared thermosetting resin composition was poured onto a hot plate of an automatic curing time measuring device, which had been heated to 80°C or 100°C, and stirred. The curing time was measured and evaluated, with the time taken from when the stirring torque was less than 1% (0.04 mN·m) immediately after stirring began until the stirring torque exceeded 50% (0.86 mN·m). The results are shown in Table 1.

[0458] [Examples 2-11, Comparative Examples 1-2] Thermosetting resin compositions were prepared in the same manner as in Example 1, except that the blocking agent dissociation catalyst in Example 1 was replaced with that shown in Examples A-2 to A-11, or comparative production examples A-1 and 1. The curing time was then measured and evaluated. The results are shown in Table 5.

[0459] [Table 5]

Claims

1. A blocking agent dissociation catalyst for blocked isocyanates containing an onium salt represented by the following formula (1). Formula (1): 【Chemistry 1】 (In the formula, n is an integer greater than or equal to 1. R １ , R ２ and R ３ A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. A represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group when n=1, and a substituted or unsubstituted n-valent hydrocarbon group when n is an integer of 2 or more. １ , R ２ , and R ３ Some or all of the atoms may be bonded to each other to form a ring structure. X represents a carbon atom, a nitrogen atom, or an oxygen atom. a represents 0 or 1. b represents 0 or 1. If X is a carbon atom, then a=1 and b=1. If X is a nitrogen atom, then a=1 and b=0. If X is an oxygen atom, then a=0 and b=0. Q ＋ (This indicates a cation.)

2. In equation (1), Q ＋ The blocking agent dissociation catalyst for blocked isocyanates according to claim 1, wherein is an organic cation.

3. In formula (1), Q ＋ The block agent dissociation catalyst for blocked isocyanate according to claim 1 or 2, wherein is an organic cation represented by the following formula (2) or the following formula (3). Formula (2): 【Chemistry 2】 (In the formula, R ４ , R ５ , R ６ and R ７ R represents identical or different substituted or unsubstituted hydrocarbon groups. ４ , R ５ , R ６ and R ７ Some or all of these may be bonded to each other to form a ring structure. ＋ (This indicates a nitrogen cation or a phosphorus cation.) Formula (3): 【Transformation 3】 (In the formula, R ８ , R ９ and R １１ R represents the same or different substituted or unsubstituted hydrocarbon groups. １０ R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. ８ , R ９ , R １０ and R １１ These may be partially or entirely bonded to each other to form a ring structure. ＋ (This indicates a nitrogen cation or a phosphorus cation.)

4. Y ＋ The blocking agent dissociation catalyst for blocked isocyanates according to claim 3, wherein is a nitrogen cation, or the organic cation represented by formula (3) is an organic cation represented by formula (3-1) or formula (3-2). Formula (3-1): 【Chemistry 4】 (In the formula, R ９ and R １２ R represents a substituted or unsubstituted hydrocarbon group. １０ , R １３ and R １４ R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. ９ , R １０ , R １２ , R １３ and R １４ (Some or all of these may be bonded to each other to form a ring structure.) Formula (3-2): 【Transformation 5】 (In the formula, R ９ R represents a substituted or unsubstituted hydrocarbon group. １０ , R １５ , R １６ , R １７ and R １８ R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. ９ , R １０ , R １５ , R １６ , R １７ and R １８ (Some or all of these may be bonded to each other to form a ring structure.)

5. The blocking agent dissociation catalyst for blocked isocyanates according to claim 1, wherein when n=1, A is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted alicyclic hydrocarbon group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic aliphatic hydrocarbon group, and when n is an integer of 2 or more, A is a substituted or unsubstituted n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent alicyclic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, or a substituted or unsubstituted n-valent aromatic aliphatic hydrocarbon group.

6. The blocking agent dissociation catalyst for blocked isocyanates according to claim 1 or 2, wherein n is an integer from 1 to 20.

7. If X is a carbon atom, then R １ , R ２ and R ３ R is the same or different hydrogen atom, or a substituted or unsubstituted alkyl group, and when X is a nitrogen atom, １ and R ２ R is the same or different hydrogen atom, or a substituted or unsubstituted alkyl group, and when X is an oxygen atom, １ The blocking agent dissociation catalyst for blocked isocyanates according to claim 1 or 2, wherein is a substituted or unsubstituted alkyl group.

8. A blocked isocyanate composition comprising a blocked isocyanate dissociation catalyst and a blocked isocyanate compound according to claim 1 or 2.

9. The blocked isocyanate composition according to claim 8, wherein the blocked isocyanate compound is a blocked isocyanate compound that has been blocked with at least one blocking agent selected from the group consisting of alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds.

10. The blocked isocyanate composition according to claim 8, wherein the blocked isocyanate compound is a blocked isocyanate compound blocked with a fluorine alcohol compound.

11. A thermosetting resin composition comprising the blocked isocyanate composition according to claim 8 and a compound having an isocyanate-reactive group.

12. The thermosetting resin composition according to claim 11, wherein the compound having an isocyanate reactive group is a polyol compound.

13. A cured product obtained by curing the thermosetting resin composition described in claim 11.

14. A method for producing a cured product, comprising the step of heating and curing the thermosetting resin composition described in claim 11.

15. Onium salts represented by the following formula (1) (excluding 1,3-diisopropyl-4,5-dimethylimidazolium N,N'-diphenylurate). Formula (1): 【Transformation 6】 (In the formula, n is 1. R １ , R ２ , and R ３ A represents a hydrogen atom, or a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, either identical or different. A represents a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 200 carbon atoms. X represents a carbon atom, a nitrogen atom, or an oxygen atom. a represents 0 or 1. b represents 0 or 1. If X is a carbon atom, then a=1 and b=1. If X is a nitrogen atom, then a=1 and b=0. If X is an oxygen atom, then a=0 and b=0. Q ＋ (This represents an organic cation represented by the following formula (2) or formula (3).) Formula (2): 【Transformation 7】 (In the formula, R ４ R is a methyl group, ５ , R ６ and R ７ R represents a hydrocarbon group having 1 to 30 carbon atoms, which may be identical or different, substituted or unsubstituted. ４ , R ５ , R ６ and R ７ Some or all of these may be bonded to each other to form a ring structure. ＋ (This indicates a nitrogen cation or a phosphorus cation.) Formula (3): 【Transformation 8】 (In the formula, R ８ , R ９ , and R １１ R represents the same or different substituted or unsubstituted hydrocarbon groups. １０ R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. ８ , R ９ , R １０ , and R １１ These may be partially or entirely bonded to each other to form a ring structure. ＋ (This indicates a nitrogen cation or a phosphorus cation.)

16. Y ＋ The onium salt according to claim 15, wherein is a nitrogen cation, or the organic cation represented by formula (3) is an organic cation represented by formula (3-1) or formula (3-2). Formula (3-1): 【Chemistry 9】 (In the formula, R ９ and R １２ R represents a substituted or unsubstituted hydrocarbon group. １０ , R １３ and R １４ R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. ９ , R １０ , R １２ , R １３ and R １４ (Some or all of these may be bonded to each other to form a ring structure.) Formula (3-2): 【Chemistry 10】 (wherein, R ９ represents a substituted or unsubstituted hydrocarbon group. R １０ , R １５ , R １６ , R １７ and R １８ are the same or different and each represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. R ９ , R １０ , R １５ , R １６ , R １７ and R １８ may be partially or wholly bonded to each other to form a ring structure.)

17. The onium salt according to claim 15, having one anion selected from (4-1) to (4-4) and one organic cation selected from (b-i) or (b-ii). Formula (4-1): 【Chemistry 11】 (In the formula, A １ R represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms. １ａ (This indicates a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 30 carbon atoms.) Formula (4-2): 【Chemistry 12】 (In the formula, A ２ and R １ａ (This represents the same or different substituted or unsubstituted aliphatic hydrocarbon groups having 1 to 30 carbon atoms.) Formula (4-3): 【Chemistry 13】 (In the formula, A １ and R １ａ (As defined above.) Formula (4-4): 【Chemistry 14】 (In the formula, A ２ and R １ａ (As defined above.) (b-i) Organic cation represented by the following formula (2) Formula (2): 【Chemistry 15】 (In the formula, R ４ R is a methyl group, ５ , R ６ and R ７ R represents a hydrocarbon group having 1 to 30 carbon atoms, which may be identical or different, substituted or unsubstituted. ４ , R ５ , R ６ and R ７ Some or all of these may be bonded to each other to form a ring structure. ＋ (This indicates a nitrogen cation or a phosphorus cation.) (b-ii) Organic cation represented by the following formula (3-1) Formula (3-1): 【Chemistry 16】 (In the formula, R ９ and R １２ R represents a substituted or unsubstituted hydrocarbon group. １０ , R １３ and R １４ R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. ９ , R １０ , R １２ , R １３ and R １４ (Some or all of these may be bonded to each other to form a ring structure.)

18. The onium salt according to claim 15, having one anion selected from (a-i) to (a-vi) and one organic cation selected from (b-i) or (b-ii). 【Chemistry 17】 (b-i) Organic cation represented by the following formula (2) Formula (2): [Chemistry 18] (In the formula, R ４ R is a methyl group, ５ , R ６ and R ７ R represents a hydrocarbon group having 1 to 30 carbon atoms, which may be identical or different, substituted or unsubstituted. ４ , R ５ , R ６ and R ７ Some or all of these may be bonded to each other to form a ring structure. ＋ (This indicates a nitrogen cation or a phosphorus cation.) (b-ii) Organic cation represented by the following formula (3-1) Formula (3-1): 【Chemistry 19】 (In the formula, R ９ and R １２ R represents a substituted or unsubstituted hydrocarbon group. １０ , R １３ and R １４ R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, either identical or different. ９ , R １０ , R １２ , R １３ and R １４ (Some or all of these may be bonded to each other to form a ring structure.)

19. The onium salt according to claim 15, wherein the onium salt is one of the following: 【Chemistry 20】

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