阅读说明：本技术 酰胺类化合物的制造方法及酰胺类化合物 (Process for producing amide compound, and amide compound ) 是由 宫城元嘉 小野田光贵 新田晋吾 于 2019-09-27 设计创作，主要内容包括：一种式(4)所表示的酰胺类化合物的制造方法,其使式(1)所表示的亚胺鎓盐与下述式(3)所表示的有机化合物发生反应(式(1)、式(3)及式(4)如说明书所记载)。(A process for producing an amide compound represented by formula (4), which comprises reacting an iminium salt represented by formula (1) with an organic compound represented by formula (3) (the formulae (1), (3) and (4) are as defined in the specification).)

1. A method for producing an amide compound, wherein an iminium salt represented by the following formula (1) is reacted with an organic compound represented by the following formula (3), the amide compound being represented by the formula (4);

formula (1):

D-H G^- (1)

in the formula (1), G^-Represents an anion; d is a nitrogen-containing organic group represented by the formula (2),

formula (2):

in the formula (2), R¹、R²、R³And R⁴Identical or different, represents a hydrocarbon radical comprising or not comprising heteroatoms; furthermore, R¹、R²、R³And R⁴Partially or totally bonding to each other to form a ring structure, or not bonding to form a ring structure;

formula (3):

in the formula (3), A represents a substituted or unsubstituted hydrocarbon group; n is an integer of 1 or more; q is-NCO or-NHCO₂R⁷Radical, R⁷Is a substituted or unsubstituted hydrocarbyl group;

formula (4):

in formula (4), A, D and n are the same as described above.

2. The process for producing an amide-based compound according to claim 1, wherein the nitrogen-containing organic group represented by formula (2) is a nitrogen-containing organic group represented by any one of the following formulae (2-1), (2-2) and (2-3);

formula (2-1):

in the formula (2-1), R¹And R⁴The same as above; r⁹And R¹⁰The same or different, hydrogen atom, or C1-6 alkyl group with or without hetero atom;

formula (2-2):

in the formula (2-2), R¹And R⁴The same as above; r¹¹And R¹²The same or different, hydrogen atom, or C1-6 alkyl group with or without hetero atom;

formula (2-3):

in the formula (2-3), R¹And R⁴The same as above; r¹³、R¹⁴、R¹⁵And R¹⁶The same or different, hydrogen atom, or C1-6 hydrocarbon group with or without hetero atom.

3. The process for producing an amide compound according to claim 1 or 2, wherein the organic compound represented by formula (3) is represented by any one of the following formula (3-1), formula (3-2), and formula (3-3);

formula (3-1):

R⁵-Q (3-1)

in the formula (3-1), Q is the same as described above; r⁵Is a substituted or unsubstituted hydrocarbyl group;

formula (3-2):

Q-R⁶-Q (3-2)

in the formula (3-2), Q is the same as described above; r⁶Is a substituted or unsubstituted hydrocarbyl group;

formula (3-3):

in the formula (3-3), Q is the same as described above; e¹、E²And E³Each independently represents a substituted or unsubstituted hydrocarbon group, or a halogen atom, alkylamino group, dialkylamino group, alkoxy group, aryloxy group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, or isocyanate group; f and g each independently represent an integer of 0 to 4; a and b are 0 or 1, c, d and e each independently represent an integer of 0 to 4; wherein, when f is 0, at least one of a and b is 1.

4. The process for producing an amide compound according to claim 1 to 3, wherein Q is-NHCO₂R⁷And (4) a base.

5. The process for producing an amide compound according to claim 1 to 4, wherein G is^-A carboxylate ion represented by the following formula (5);

formula (5):

in the formula (5), R⁸Represents a hydrogen atom, a hydroxyl group, an alkoxy group, a fluoroalkyl group, or a hydrocarbon group with or without a heteroatom.

6. The method for producing an amide compound according to claim 1 to 5, wherein A is an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent selected from at least one of a halogen atom, an alkylamino group, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, an (alkylamino) carbonylamino group, a (dialkylamino) carbonylamino group, and an isocyanate group.

7. The process for producing an amide compound according to claim 1 to 6, wherein n is an integer of 1 to 6.

8. An amide compound represented by the formula (4) wherein 4, 5-dimethyl-1, 3-diisopropylimidazolium-2-N- (p-isopropylphenyl) amide salt, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium-2-N- (1-adamantyl) amide salt, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium-2-N-phenylamide salt are excluded;

formula (4):

in the formula (4), A represents a substituted or unsubstituted hydrocarbon group; n is an integer of 1 or more; d is a nitrogen-containing organic group represented by the formula (2),

formula (2):

in the formula (2), R¹And R⁴The same or different, and is a C2-30 hydrocarbon group containing or not containing hetero atoms; r²And R³The same as above; furthermore, R¹、R²、R³And R⁴Some or all of which are bonded to each other to form a ring structure, or are not bonded to form a ring structure.

9. The amide-based compound according to claim 8, wherein A is an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent selected from at least one of a halogen atom, an alkylamino group, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, an (alkylamino) carbonylamino group, a (dialkylamino) carbonylamino group, and an isocyanate group.

10. The amide-based compound according to claim 8 or 9, wherein n is an integer of 1 to 6.

11. The amide-based compound according to claim 8, wherein the amide-based compound represented by formula (4) is represented by any one of the following formula (4-1), formula (4-2) and formula (4-3);

formula (4-1):

in the formula (4-1), R⁵Is a substituted or unsubstituted hydrocarbyl group; d is the same as above;

formula (4-2):

in the formula (4-2), R⁶Is a substituted or unsubstituted hydrocarbyl group; d is the same as above;

formula (4-3):

in the formula (4-3), D is the same as above; e¹、E²And E³Each independently represents a substituted or unsubstituted hydrocarbon group, or a halogen atom, alkylamino group, dialkylamino group, alkoxy group, aryloxy group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, or isocyanate group; f and g each independently represent an integer of 0 to 4; a and b are 0 or 1, c, d and e each independently represent an integer of 0 to 4; wherein, when f is 0, at least one of a and b is 1.

12. The amide-based compound according to claim 8 to 11, wherein the nitrogen-containing organic group represented by formula (2) is a nitrogen-containing organic group represented by any one of the following formulae (2-1), (2-2), and (2-3);

formula (2-1):

in the formula (2-1), R¹And R⁴The same as above; r⁹And R¹⁰The same or different, hydrogen atom, or C1-6 alkyl group with or without hetero atom;

formula (2-2):

in the formula (2-2), R¹And R⁴The same as above; r¹¹And R¹²The same or different, hydrogen atom, or C1-6 alkyl group with or without hetero atom;

formula (2-3):

in the formula (2-3), R¹And R⁴The same as above; r¹³、R¹⁴、R¹⁵And R¹⁶The same or different, hydrogen atom, or C1-6 hydrocarbon group with or without hetero atom.

13. A blocked dissociation catalyst for blocked isocyanates, which comprises an amide compound represented by the formula (4);

formula (4):

in the formula (4), A represents a substituted or unsubstituted hydrocarbon group; n is an integer of 1 or more; d is a nitrogen-containing organic group represented by formula (2);

formula (2):

in the formula (2), R¹And R⁴The same or different, represent a hydrocarbon group of 2 to 30 carbon atoms, which may or may not contain a hetero atom; r²And R³Identical or different, represents a hydrocarbon radical comprising or not comprising heteroatoms; furthermore, R¹、R²、R³And R⁴Some or all of which are bonded to each other to form a ring structure, or are not bonded to form a ring structure.

14. A thermosetting composition comprising the blocked dissociation catalyst for blocked isocyanates according to claim 13, a blocked isocyanate, and a compound having an isocyanate-reactive group.

Technical Field

The present invention relates to a method for producing an amide Compound (amide Compound) and an amide Compound.

Background

As a conventional method for producing an amide-based compound, (1) a method of reacting an alkyl imidazole with dimethyl carbonate to produce CO is known₂Addition product of CO₂A method of reacting the adduct with an isocyanate compound (patent document 1); (2) a method of reacting a dialkyl imidazolium carbene with an isocyanate compound (non-patent document 1).

Further, the amide-based compound described in patent document 1 is useful as a catalyst for urethane polymerization. In the amide-based compound described in patent document 1, at least one of the substituents on the nitrogen atom of the heterocyclic skeleton must be a methyl group as a primary carbon.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2018/025970

Non-patent document

Non-patent document l: struct. chem.2013 24 volume 2059-206 page

Disclosure of Invention

Problems to be solved by the invention

However, the method (1) described in patent document 1 generally requires a reaction temperature equal to or higher than the boiling point of dimethyl carbonate, and therefore requires a pressure reaction apparatus. On the other hand, the method (2) described in non-patent document 1 requires production of NHC carbene, but in general, since carbene is an unstable compound to oxygen and water and needs to be handled in a special facility such as a glove box, it is not preferable from a practical point of view. Further, if the NHC carbene is not highly stable as if the substituent on the nitrogen atom of the heterocyclic skeleton is an isopropyl group, it is difficult to separate the carbene, and therefore, the substituent on the nitrogen atom of the heterocyclic skeleton is limited in the method (2) above, and it is difficult to produce an amide compound other than the specific compound with respect to the amide compound to be produced.

Further, the present inventors have found that the amide-based compound 1-methyl-3-octylimidazolium-2-N-phenylamide salt (OMIm-PI) described in patent document 1 is not preferable in terms of compatibility with a mixture of a blocked isocyanate and a compound having an isocyanate-reactive group, which are raw materials of a thermosetting composition, and as a result, the OMIm-PI is used as a catalyst (blocking dissociation catalyst) for urethane polymerization of a thermosetting resin, and still needs to be improved (see reference example 1 described later).

The present invention has been made in view of the above background art, and has an object to: (I) to provide a process for producing an amide-based compound without requiring any special equipment such as a pressure reaction apparatus and a glove box; and (II) a novel amide compound having improved compatibility with a thermosetting composition raw material.

Means for solving the problems

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that (I) a corresponding amide-based compound can be obtained from an iminium salt capable of easily introducing various substituents to the nitrogen atom without requiring any special equipment, and (II) an amide-based compound (4) producible by the present production method, particularly R of a nitrogen-containing organic group represented by formula (2)¹And R⁴The amide-based compound having 2 to 30 carbon atoms has improved compatibility with a thermosetting composition raw material, and the present invention has been completed.

That is, the present invention includes the following [1] to [14 ].

[1] A method for producing an amide compound, which comprises reacting an iminium salt represented by the following formula (1) with an organic compound represented by the following formula (3), wherein the amide compound is represented by the formula (4);

formula (1):

[ solution 1]

D-H G^- (1)

In the formula (1), G^-Represents an anion; d is a nitrogen-containing organic group represented by the formula (2),

formula (2):

[ solution 2]

In the formula (2), R¹、R²、R³And R⁴The same or different, indicates that a hetero atom may be containedA hydrocarbyl group of a molecule; furthermore, R¹、R²、R³And R⁴May be partially or wholly bonded to each other to form a ring structure;

formula (3):

[ solution 3]

In the formula (3), A represents a substituted or unsubstituted hydrocarbon group; n is an integer of 1 or more; q is-NCO or-NHCO₂R⁷Radical, R⁷Is a substituted or unsubstituted hydrocarbyl group;

formula (4):

[ solution 4]

In formula (4), A, D and n are the same as described above.

[2] The process for producing an amide compound according to [1], wherein the nitrogen-containing organic group represented by the formula (2) is a nitrogen-containing organic group represented by any one of the following formulae (2-1), (2-2) and (2-3);

formula (2-1):

[ solution 5]

In the formula (2-1), R¹And R⁴The same as above; r⁹And R¹⁰The same or different, hydrogen atom or C1-C6 alkyl group which can contain hetero atom;

formula (2-2):

[ solution 6]

In the formula (2-2), R¹And R⁴The same as above; r¹¹And R¹²The same or different, hydrogen atom or C1-C6 alkyl group which can contain hetero atom;

formula (2-3):

[ solution 7]

In the formula (2-3), R¹And R⁴The same as above; r¹³、R¹⁴、R¹⁵And R¹⁶The same or different, and is a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms which may contain a hetero atom.

[3] The process for producing an amide compound according to [1] or [2], wherein the organic compound represented by the formula (3) is represented by any one of the following formulae (3-1), (3-2) and (3-3);

formula (3-1):

[ solution 8]

R⁵-Q (3-1)

In the formula (3-1), Q is the same as described above; r⁵Is a substituted or unsubstituted hydrocarbyl group;

formula (3-2):

[ solution 9]

Q-R⁶-Q (3-2)

In the formula (3-2), Q is the same as described above; r⁶Is a substituted or unsubstituted hydrocarbyl group;

formula (3-3):

[ solution 10]

In the formula (3-3), Q is the same as described above; e¹、E²And E³Each independently represents a substituted or unsubstituted hydrocarbon group, or a halogen atom, alkylamino group, dialkylamino group, alkoxy group, aryloxy group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, or isocyanate group; f and g each independently represent an integer of 0 to 4; a and b are 0 or 1, c, d and e are each independentlyGround represents an integer of 0 to 4; wherein, when f is 0, at least one of a and b is 1.

[4]According to [1]～[3]The process for producing the amide compound, wherein Q is-NHCO₂R⁷And (4) a base.

[5]According to [1]～[4]The process for producing the amide compound, wherein G^-A carboxylate ion represented by the following formula (5);

formula (5):

[ solution 11]

In the formula (5), R⁸Represents a hydrogen atom, a hydroxyl group, an alkoxy group, a fluoroalkyl group or a hydrocarbon group which may contain a hetero atom.

[6] The process for producing an amide compound according to [1] to [5], wherein A is an unsubstituted hydrocarbon group or a hydroxyl group having a substituent selected from at least one of a halogen atom, an alkylamino group, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, an (alkylamino) carbonylamino group, a (dialkylamino) carbonylamino group, and an isocyanate group.

[7] The process for producing an amide-based compound according to any one of [1] to [6], wherein n is an integer of 1 to 6.

[8] An amide compound represented by the formula (4) wherein 4, 5-dimethyl-1, 3-diisopropylimidazolium-2-N- (p-isopropylphenyl) amide salt, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium-2-N- (1-adamantyl) amide salt, 1, 3-bis (2, 6-diisopropylphenyl) imidazolium-2-N-phenylamide salt are excluded;

formula (4):

[ solution 12]

In the formula (4), A represents a substituted or unsubstituted hydrocarbon group; n is an integer of 1 or more; d is a nitrogen-containing organic group represented by the formula (2).

Formula (2):

[ solution 13]

In the formula (2), R¹And R⁴The same or different, is a hydrocarbon group of 2-30 carbon atoms which may contain hetero atoms; r²And R³The same as above; furthermore, R¹、R²、R³And R⁴May be partially or wholly bonded to each other to form a ring structure.

[9] The amide-based compound according to [8], wherein A is an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent selected from at least one of a halogen atom, an alkylamino group, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, an (alkylamino) carbonylamino group, a (dialkylamino) carbonylamino group, and an isocyanate group.

[10] The amide-based compound according to [8] or [9], wherein n is an integer of 1 to 6.

[11] The amide-based compound according to [8], wherein the amide-based compound represented by the formula (4) is represented by any one of the following formulae (4-1), (4-2) and (4-3);

formula (4-1):

[ solution 14]

In the formula (4-1), R⁵Is a substituted or unsubstituted hydrocarbyl group; d is the same as above;

formula (4-2):

[ solution 15]

In the formula (4-2), R⁶Is a substituted or unsubstituted hydrocarbyl group; d and the above phasesThe same is carried out;

formula (4-3):

[ solution 16]

In the formula (4-3), D is the same as above; e¹、E²And E³Each independently represents a substituted or unsubstituted hydrocarbon group, or a halogen atom, alkylamino group, dialkylamino group, alkoxy group, aryloxy group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, or isocyanate group; f and g each independently represent an integer of 0 to 4; a and b are 0 or 1, c, d and e each independently represent an integer of 0 to 4; wherein, when f is 0, at least one of a and b is 1.

[12] The amide-based compound according to [8] to [11], wherein the nitrogen-containing organic group represented by the formula (2) is a nitrogen-containing organic group represented by any one of the following formulae (2-1), (2-2), and (2-3);

formula (2-1):

[ solution 17]

In the formula (2-1), R¹And R⁴The same as above; r⁹And R¹⁰The same or different, hydrogen atom or C1-C6 alkyl group which can contain hetero atom;

formula (2-2):

[ solution 18]

In the formula (2-2), R¹And R⁴The same as above; r¹¹And R¹²The same or different, hydrogen atom or C1-C6 alkyl group which can contain hetero atom;

formula (2-3):

[ solution 19]

In the formula (2-3), R¹And R⁴The same as above; r¹³、R¹⁴、R¹⁵And R¹⁶The same or different, and is a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms which may contain a hetero atom.

[13] A blocked dissociation catalyst for blocked isocyanates, which comprises an amide compound represented by the formula (4);

formula (4):

[ solution 20]

In the formula (4), A represents a substituted or unsubstituted hydrocarbon group; n is an integer of 1 or more, D is a nitrogen-containing organic group represented by the formula (2);

formula (2):

[ solution 21]

In the formula (2), R¹And R⁴The same or different, represent a hydrocarbon group of 2 to 30 carbon atoms which may contain a heteroatom; r²And R³Identical or different, represent a hydrocarbon group which may contain heteroatoms; furthermore, R¹、R²、R³And R⁴May be partially or wholly bonded to each other to form a ring structure.

[14] A thermosetting composition comprising the blocked dissociation catalyst for blocked isocyanates according to [13], a blocked isocyanate, and a compound having an isocyanate-reactive group.

Effects of the invention

According to the present invention, there can be provided (I) a process for producing an amide-based compound, which can produce a compound having various substituents on a nitrogen atom of a heterocyclic skeleton of the amide-based compound without requiring any special equipment such as a pressure reaction apparatus and a glove box; and (II) a novel amide compound having improved compatibility with the raw material for thermosetting compositions.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail.

< Process for producing amide-based Compound >

First, an iminium salt represented by formula (1) (hereinafter referred to as an iminium salt (1)) will be described.

In the formula (1), G^-Represents an anion. D is a nitrogen-containing organic group represented by the formula (2). The anion is not particularly limited as long as it can form a salt with the imine cation represented by formula (2), and examples thereof include: carboxylate ions, halogen ions, sulfonate ions, phosphate ions and the like, and preferably carboxylate ions represented by the following formula (5).

Formula (5):

[ solution 22]

In the formula (5), R⁸Represents a hydrogen atom, a hydroxyl group, an alkoxy group, a fluoroalkyl group or a hydrocarbon group which may contain a hetero atom.

In the formula (5), R⁸Represents a hydrogen atom, a hydroxyl group, an alkoxy group, a fluoroalkyl group or a hydrocarbon group which may contain a hetero atom. Preferably a hydroxyl group or a hydrocarbon group which may contain a heteroatom, more preferably a hydrocarbon group which may contain a heteroatom. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an alkoxy group having 1 or 2 carbon atoms. The fluoroalkyl group is preferably a fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a fluoroalkyl group having 1 to 4 carbon atoms. As the hydrocarbon group which may contain a hetero atom (i.e., a hetero atom-containing group or a hetero atom-free group), a hydrocarbon group having 1 to 6 carbon atoms is preferable, and a hydrocarbon group having 1 to 6 carbon atoms which does not contain a hetero atom is particularly preferable.

In the present specification, examples of the hetero atom include: nitrogen atom, oxygen atom, sulfur atom, and the like.

Examples of the carboxylate ion represented by formula (5) include: formate ion, acetate ion, propionate ion, butyrate ion, methoxyacetate ion, ethoxyacetate ion, propoxyethoxyacetate ion, 2- (2-methoxyethoxy) acetate ion, 2- (2-ethoxyethoxy) acetate ion, 2- (2-propoxyethoxy) acetate ion, 3-methoxypropionate ion, 3-ethoxypropionate ion, 3- (2-methoxyethoxy) propionate ion, 3- (2-ethoxyethoxy) propionate ion, 3- (2-propoxyethoxy) propionate ion, 3- (3-methoxypropoxy) propionate ion, 3- (3-ethoxypropoxy) propionate ion, 3- (3-propoxypropoxy) propionate ion, propionate ion, Carboxylate ions such as oleate ions, linoleate ions, sorbate ions, benzoate ions, phthalate ions, isophthalate ions, terephthalate ions, lactate ions, salicylate ions, and trifluoroacetic acid ions; alkyl carbonate ions such as methyl carbonate ion and ethyl carbonate ion; and bicarbonate ions and the like.

Examples of the halogen ion include: chloride ion, bromide ion, iodide ion, etc., preferably chloride ion.

Examples of the sulfonate ion include: methanesulfonate ion, trifluoromethanesulfonate ion, nonafluorobutanesulfonate ion, benzenesulfonate ion, p-toluenesulfonate ion and the like, preferably methanesulfonate ion.

Examples of the phosphate ion include: dimethyl phosphate ion, diethyl phosphate ion, dibutyl phosphate ion, and the like, and dimethyl phosphate ion is preferable.

The nitrogen-containing organic group represented by formula (2) (hereinafter referred to as nitrogen-containing organic group (2)) will be described.

In the formula (2), R¹、R²、R³And R⁴Is a hydrocarbon group which may contain a hetero atom, preferably a hydrocarbon group of 1 to 30 carbon atoms which may contain a hetero atom, more preferably a hydrocarbon group of 1 to 20 carbon atoms which may contain a hetero atom, and particularly preferably a hydrocarbon group which may contain a hetero atomA hydrocarbon group having 1 to 9 carbon atoms. R¹、R²、R³And R⁴May be partially or wholly bonded to each other to form a ring structure. For example, R¹And R²、R²And R³、R³And R⁴、R²、R³And R⁴Or R¹、R²、R³And R⁴May be bonded to each other to form a ring structure. Examples of the hydrocarbon group which may contain a hetero atom include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, allyl, benzyl, cyclohexyl, adamantyl, phenyl, 2, 6-diisopropylphenyl, 2,4, 6-trimethylphenyl, 2-methoxyethyl, 2-ethoxyethyl, and 2- (dimethylamino) ethyl, and the like. Preferred are methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, octadecyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, benzyl, phenyl, and 2,4, 6-trimethylphenyl groups, and particularly preferred are methyl, ethyl, butyl, octyl, 2-ethylhexyl, and benzyl groups.

In another embodiment of the present invention, R¹And R⁴The same or different, is a C2-30 hydrocarbon group which may contain a hetero atom, preferably a C7-30 hydrocarbon group, more preferably a C7-20 hydrocarbon group. R²And R³The same or different, represent a hydrocarbon group which may contain a heteroatom. Furthermore, R¹、R²、R³And R⁴May be partially or wholly bonded to each other to form a ring structure.

In the present invention, R of the nitrogen-containing organic group (2)²And R³Preferably bonded to each other to form a ring structure. The nitrogen-containing organic group (2) forming a ring is preferably a nitrogen-containing organic group represented by any one of the formulae (2-1), (2-2) and (2-3), and particularly preferably a nitrogen-containing organic group represented by the formula (2-1).

In the formula (2-1), R¹And R⁴As described above. R⁹And R¹⁰Is a hydrogen atom or a carbon number of 1 to E which may contain hetero atomsThe hydrocarbon group of 6 is preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, phenyl, 2-methoxyethyl, 2-ethoxyethyl, and 2- (dimethylamino) ethyl groups, etc., preferably methyl.

In the present specification, unless otherwise specified, the expressions propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, dodecyl, tetradecyl, hexadecyl, and octadecyl denote straight-chain alkyl groups such as n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.

Specific examples of the nitrogen-containing organic group (2-1) include: 1, 3-dimethylimidazolium group, 1-ethyl-3-methylimidazolium group, 1-methyl-3-propylimidazolium group, 1-methyl-3-isopropylimidazolium group, 1-butyl-3-methylimidazolium group, 1-tert-butyl-3-methylimidazolium group, 1-hexyl-3-methylimidazolium group, 1-cyclohexyl-3-methylimidazolium group, 1-methyl-3-octylimidazolium group, 1-methyl-3- (2-ethylhexyl) imidazolium group, 1-dodecyl-3-methylimidazolium group, 1-methyl-3-tetradecylimidazolium group, 1-hexadecyl-3-methylimidazolium group, 1-methyl-3-octadecylimidazolium group, 1-allyl-3-methylimidazolium group, 1-benzyl-3-methylimidazolium group, 1-methyl-3-phenylimidazolium group, 1-methyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-mesityl-3-methylimidazolium group;

1, 3-diethylimidazolium group, 1-ethyl-3-propylimidazolium group, 1-ethyl-3-isopropylimidazolium group, 1-butyl-3-ethylimidazolium group, 1-ethyl-3-tert-butylimidazolium group, 1-ethyl-3-hexylmethylimidazolium group, 1-ethyl-3-cyclohexylmethylimidazolium group, 1-ethyl-3-octylimidazolium group, 1-ethyl-3- (2-ethylhexyl) imidazolium group, 1-ethyl-3-dodecylimidazolium group, 1-ethyl-3-tetradecylimidazolium group, 1-ethyl-3-hexadecylimidazolium group, 1-ethyl-3-octadecylimidazolium group, 1-allyl-3-ethylimidazolium group, 1-benzyl-3-ethylimidazolium group, 1-ethyl-3-phenylimidazolium group, 1-ethyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-ethyl-3-mesitylimidazolium group;

1, 3-dipropylimidazolium group, 1-propyl-3-isopropylimidazolium group, 1-butyl-3-propylimidazolium group, 1-tert-butyl-3-propylimidazolium group, 1-hexyl-3-propylimidazolium group, 1-cyclohexyl-3-propylimidazolium group, 1-octyl-3-propylimidazolium group, 1- (2-ethylhexyl) -3-propylimidazolium group, 1-dodecyl-3-propylimidazolium group, 1-propyl-3-tetradecylimidazolium group, 1-hexadecyl-3-propylimidazolium group, 1-octadecyl-3-propylimidazolium group, 1-allyl-3-propylimidazolium group, 1-tert-butyl-3-propylimidazolium group, 1-benzyl-3-propylimidazolium group, 1-phenyl-3-propylimidazolium group, 1-propyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-mesityl-3-propylimidazolium group;

1, 3-diisopropylimidazolium group, 1-butyl-3-isopropylimidazolium group, 1-tert-butyl-3-isopropylimidazolium group, 1-hexyl-3-isopropylimidazolium group, 1-cyclohexyl-3-isopropylimidazolium group, 1-octyl-3-isopropylimidazolium group, 1- (2-ethylhexyl) -3-isopropylimidazolium group, 1-dodecyl-3-isopropylimidazolium group, 1-isopropyl-3-tetradecylimidazolium group, 1-hexadecyl-3-isopropylimidazolium group, 1-octadecyl-3-isopropylimidazolium group, 1-allyl-3-isopropylimidazolium group, 1-tert-butyl-3-isopropylimidazolium group, 1-benzyl-3-isopropylimidazolium group, 1-phenyl-3-isopropylimidazolium group, 1-isopropyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-mesityl-3-isopropylimidazolium group;

1, 3-dibutylimidazolium group, 1-butyl-3-tert-butylimidazolium group, 1-butyl-3-hexylmethylimidazolium group, 1-butyl-3-octylimidazolium group, 1-butyl-3- (2-ethylhexyl) imidazolium group, 1-butyl-3-dodecylimidazolium group, 1-butyl-3-tetradecylimidazolium group, 1-butyl-3-hexadecylimidazolium group, 1-butyl-3-cyclohexadecylimidazolium group, 1-butyl-3-octadecylimidazolium group, 1-allyl-3-butylimidazolium group, 1-benzyl-3-butylimidazolium group, 1-butyl-3-butylimidazolium group, 1-butyl-3-phenylimidazolium group, 1-butyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-butyl-3-mesitylimidazolium group;

1, 3-di (t-butyl) imidazolium group, 1-t-butyl-3-hexylmethylimidazolium group, 1-t-butyl-3-cyclohexylmethylimidazolium group, 1-t-butyl-3-octylimidazolium group, 1-t-butyl-3- (2-ethylhexyl) imidazolium group, 1-t-butyl-3-dodecylimidazolium group, 1-t-butyl-3-tetradecylimidazolium group, 1-t-butyl-3-hexadecylimidazolium group, 1-t-butyl-3-octadecylimidazolium group, 1-allyl-3-t-butylimidazolium group, 1-benzyl-3-t-butylimidazolium group, 1-t-butyl-3-phenylimidazolium group, 1-tert-butyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-tert-butyl-3-mesitylimidazolium group;

1, 3-dihexylimidazolium group, 1-hexyl-3-cyclohexylimidazolium group, 1- (2-ethylhexyl) -3-hexylimidazolium group, 1-dodecyl-3-hexylimidazolium group, 1-hexyl-3-tetradecylimidazolium group, 1-hexadecyl-3-hexylimidazolium group, 1-hexyl-3-octadecylimidazolium group, 1-allyl-3-hexylimidazolium group, 1-benzyl-3-hexylimidazolium group, 1-hexyl-3-phenylimidazolium group, 1-hexyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-hexyl-3-mesitylimidazolium group;

1, 3-dicyclohexylimidazolium group, 1- (2-ethylhexyl) -3-cyclohexylimidazolium group, 1-dodecyl-3-cyclohexylimidazolium group, 1-cyclohexyl-3-tetradecylimidazolium group, 1-hexadecyl-3-cyclohexylimidazolium group, 1-cyclohexyl-3-octadecylimidazolium group, 1-allyl-3-cyclohexylimidazolium group, 1-benzyl-3-cyclohexylimidazolium group, 1-cyclohexyl-3-phenylimidazolium group, 1-cyclohexyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-cyclohexyl-3-mesitylimidazolium group;

1, 3-dioctylimidazolium group, 1- (2-ethylhexyl) -3-octylimidazolium group, 1-dodecyl-3-octylimidazolium group, 1-octyl-3-tetradecylimidazolium group, 1-hexadecyl-3-octylimidazolium group, 1-octadecyl-3-octylimidazolium group, 1-allyl-3-octylimidazolium group, 1-benzyl-3-octylimidazolium group, 1-phenyl-3-octylimidazolium group, 1-octyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-mesityl-3-octylimidazolium group;

1, 3-bis (2-ethylhexyl) imidazolium group, 1- (2-ethylhexyl) -3-dodecylimidazolium group, 1- (2-ethylhexyl) -3-tetradecylimidazolium group, 1- (2-ethylhexyl) -3-hexadecylimidazolium group, 1- (2-ethylhexyl) -3-octadecylimidazolium group, 1-allyl-3- (2-ethylhexyl) imidazolium group, 1-benzyl-3- (2-ethylhexyl) imidazolium group, 1- (2-ethylhexyl) -3-phenylimidazolium group, 1- (2-ethylhexyl) -3- (2, 6-diisopropylphenyl) imidazolium group, a salt thereof, a hydrate thereof, 1- (2-ethylhexyl) -3-mesitylimidazolium radical;

1, 3-didodecyl imidazolium group, 1-dodecyl-3-tetradecyl imidazolium group, 1-dodecyl-3-hexadecyl imidazolium group, 1-dodecyl-3-octadecyl imidazolium group, 1-allyl-3-dodecyl imidazolium group, 1-benzyl-3-dodecyl imidazolium group, 1-dodecyl-3-phenyl imidazolium group, 1-dodecyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-dodecyl-3-mesitylimidazolium group;

1, 3-ditetradecylimidazolium group, 1-hexadecyl-3-tetradecylimidazolium group, 1-octadecyl-3-tetradecylimidazolium group, 1-allyl-3-tetradecylimidazolium group, 1-benzyl-3-tetradecylimidazolium group, 1-phenyl-3-tetradecylimidazolium group, 1- (2, 6-diisopropylphenyl) -3-tetradecylimidazolium group, 1-mesityl-3-tetradecylimidazolium group;

1, 3-dihexadecyl imidazolium group, 1-hexadecyl-3-octadecylimidazolium group, 1-allyl-3-hexadecylimidazolium group, 1-benzyl-3-hexadecylimidazolium group, 1-hexadecyl-3-phenylimidazolium group, 1-hexadecyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-hexadecyl-3-mesitylimidazolium group;

1, 3-dioctadecyl imidazolium group, 1-allyl-3-octadecyl imidazolium group, 1-benzyl-3-octadecyl imidazolium group, 1-phenyl-3-octadecyl imidazolium group, 1- (2, 6-diisopropylphenyl) -3-octadecyl imidazolium group, 1-mesityl-3-octadecyl imidazolium group;

1, 3-diallylimidazolium group, 1-allyl-3-benzylimidazolium group, 1-allyl-3-phenylimidazolium group, 1-allyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-allyl-3-mesitylimidazolium group;

1, 3-dibenzylimidazolium group, 1-benzyl-3-phenylimidazolium group, 1-benzyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-benzyl-3-mesitylimidazolium group;

1, 3-diphenylimidazolium group, 1-phenyl-3- (2, 6-diisopropylphenyl) imidazolium group, 1-mesityl-3-phenylimidazolium group;

1, 3-bis (2, 6-diisopropylphenyl) imidazolium group, 1-phenyl-3- (2, 6-diisopropylphenyl) imidazolium group;

1, 3-ditriphenylimidazolium radical; and

1,3,4, 5-tetramethylimidazolium group and the like, preferably 1, 3-dimethylimidazolium group, 1-ethyl-3-methylimidazolium group, 1-butyl-3-methylimidazolium group, 1-methyl-3-octylimidazolium group, 1-methyl-3- (2-ethylhexyl) imidazolium group, 1-dodecyl-3-methylimidazolium group, 1-methyl-3-octadecylimidazolium group, 1-benzyl-3-methylimidazolium group, 1, 3-dibutylimidazolium group, 1-butyl-3-ethylimidazolium group, 1-butyl-3-octylimidazolium group, 1-butyl-3- (2-ethylhexyl) imidazolium group, 1-butyl-3-dodecyl-3-butylimidazolium group, 1-butyl-3-octadecylimidazolium group, 1-benzyl-3-butylimidazolium group, 1, 3-dioctylimidazolium group, 1-ethyl-3-octylimidazolium group, 1-octyl-3- (2-ethylhexyl) imidazolium group, 1-dodecyl-3-octylimidazolium group, 1-octyl-3-octadecylimidazolium group, 1-benzyl-3-octylimidazolium group, 1, 3-bis (2-ethylhexyl) imidazolium group, 1-ethyl-3- (2-ethylhexyl) imidazolium group, 1- (2-ethylhexyl) -3-dodecylimidazolium group, 1- (2-ethylhexyl) -3-octadecylium group, 1- (2-ethylhexyl) -3-octadecylimidazolium group, 1-benzyl-3- (2-ethylhexyl) imidazolium group, 1, 3-didodecyl-imidazolium group, 1-dodecyl-3-octadecylimidazolium group, 1-benzyl-3-dodecylimidazolium group, 1, 3-dioctadecyl-imidazolium group, 1-benzyl-3-octadecylimidazolium group, and 1, 3-dibenzylimidazolium group are particularly preferred, and 1-ethyl-3-methylimidazolium group, 1, 3-dibutylimidazolium group, 1, 3-dioctylimidazolium group, 1, 3-bis (2-ethylhexyl) imidazolium group, 1, 3-didodecyl-imidazolium group, And a 1, 3-dibenzylimidazolium group.

In the formula (2-2), R¹And R⁴As described above. R¹¹And R¹²Is a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms which may contain a hetero atom, and is preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, phenyl, 2-methoxyethyl, 2-ethoxyethyl, 2- (dimethylamino) ethyl and the like, with methyl being preferred.

Specifically, there may be mentioned: 1, 3-dimethylimidazolinium group, 1-ethyl-3-methylimidazolinium group, 1-methyl-3-propylimidazolinium group, 1-butyl-3-methylimidazolinium group, 1-hexyl-3-methylimidazolinium group, 1-methyl-3-octylimidazolinium group, 1-dodecyl-3-methylimidazolinium group, 1-allyl-3-methylimidazolinium group, 1-benzyl-3-methylimidazolinium group, 1-methyl-3-phenylimidazolinium group, 1-methyl-3- (2, 6-diisopropylphenyl) imidazolinium group, 1-mesityl-3-methylimidazolinium group, 1-methyl-3-methylimidazolinium group, a salt thereof, and a salt thereof, 1, 3-diethylimidazolinium, 1, 3-dipropylimidazolinium, 1, 3-diisopropylimidazolinium, 1, 3-dibutylimidazolinium, 1, 3-di-tert-butylimidazolinium, 1, 3-dioctylimidazolinium, 1, 3-diphenylimidazolinium, 1, 3-bis (2, 6-diisopropylphenyl) imidazolinium, 1, 3-ditriphenylimidazolinium, 1,3,4, 5-tetramethylimidazolinium, and 1,3,4, 5-tetramethylimidazolinium, etc., preferably 1, 3-dimethylimidazolinium, 1-ethyl-3-methylimidazolinium , 1-methyl-3-propylimidazolinium, 1-butyl-3-methylimidazolinium, And 1-methyl-3-octylimidazolinium groups, particularly preferably 1, 3-dimethylimidazolinium groups, 1-butyl-3-methylimidazolinium groups, and 1-methyl-3-octylimidazolinium groups.

In the formula (2-3), R¹And R⁴As described above. R¹³、R¹⁴、R¹⁵And R¹⁶Is a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms which may contain a hetero atom, and is preferably a hydrogen atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms which may contain a hetero atom include: methyl, ethyl, propyl, isopropyl, butylSec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, phenyl, 2-methoxyethyl, 2-ethoxyethyl, and 2- (dimethylamino) ethyl, etc., preferably methyl.

Specifically, there may be mentioned: 1, 3-dimethylbenzylimidazolium group, 1-ethyl-3-methylbenzylimidazolium group, 1-methyl-3-propylbenzimidazolium group, 1-methyl-3-isopropylbenzimidazolium group, 1-butyl-3-methylbenzylimidazolium group, 1-tert-butyl-3-methylbenzylimidazolium group, 1-hexyl-3-methylbenzylium group, 1-methyl-3-octylbenzimidazolium group, 1-dodecyl-3-methylbenzylium group, 1-allyl-3-methylbenzylium group, 1-benzyl-3-methylbenzylium group, 1, 3-diethylbenzimidazolium group, 1-ethyl-3-methylbenzylium group, 1-methyl-3-methylbenzylium group, 1-ethyl-3-methylbenzylium group, 1-methyl-3-methylbenzylium group, 1, 3-dipropylbenzimidazolium group, 1, 3-diisopropylbenzimidazolium group, 1, 3-dibutylbenzimidazolium group, 1, 3-di-tert-butylbenzimidazolium group, 1, 3-dioctylbenzimidazolium group, 1, 3-diphenylbenzimidazolium group, 1, 3-bis (2, 6-diisopropylphenyl) benzimidazolium group, 1, 3-ditriphenylbenzimidazolium group, 1,3, 6-trimethylbenzimidazolium group, 1-acetyl-3, 6-dimethylbenzylium group, 1,3,6, 7-tetramethylbenzimidazolium group, and 1, 3-dibenzyl-6, 7-dimethylbenzylimidazolium group and the like, preferably 1, 3-dimethylbenzylium group, 1-ethyl-3-methylbenzimidazolium group, 1-methyl-3-propylbenzimidazolium group and 1-butyl-3-methylbenzimidazolium group, and particularly preferably 1, 3-dimethylbenzimidazolium group.

Examples of the iminium salt (1) include: 1, 3-dimethylimidazolium formate, 1-ethyl-3-methylimidazolium formate, 1-butyl-3-methylimidazolium formate, 1-methyl-3-octylimidazolium formate, 1-methyl-3- (2-ethylhexyl) imidazolium formate, 1-dodecyl-3-methylimidazolium formate, 1-methyl-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- (2-ethylhexyl) imidazolium formate, methyl-ethyl-3-imidazolium formate, methyl-3-octadecyl-imidazolium formate, methyl-3-methylimidazolium formate, 1-butyl-, 1-butyl-3-dodecylimidazolium formate, 1-butyl-3-octadecylimidazolium formate, 1-benzyl-3-butylimidazolium formate, 1, 3-dioctylimidazolium formate, 1-ethyl-3-octylimidazolium formate, 1-octyl-3- (2-ethylhexyl) imidazolium formate, 1-dodecyl-3-octylimidazolium formate, 1-octyl-3-octadecylimidazolium formate, 1-benzyl-3-octylimidazolium formate, 1, 3-bis (2-ethylhexyl) imidazolium formate, 1-ethyl-3- (2-ethylhexyl) imidazolium formate, 1-tert-butyl-3-octylimidazolium formate, 1-ethyl-3-octadecylium formate, 1-ethyl-3-octylimidazolium formate, 1, 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-benzyl-3-dodecylimidazolium formate, 1, 3-dioctadecyl imidazolium formate, 1-benzyl-3-octadecylimidazolium formate, and 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- (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- (2-ethylhexyl) imidazolium acetate, mixtures thereof, and the like, 1-butyl-3-dodecylimidazolium acetate, 1-butyl-3-octadecylimidazolium acetate, 1-benzyl-3-butylimidazolium acetate, 1, 3-dioctylimidazolium acetate, 1-ethyl-3-octylimidazolium acetate, 1-octyl-3- (2-ethylhexyl) imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-octyl-3-octadecylimidazolium acetate, 1-benzyl-3-octylimidazolium acetate, 1, 3-bis (2-ethylhexyl) imidazolium acetate, 1-ethyl-3- (2-ethylhexyl) imidazolium acetate, 1-benzyl-3-octylimidazolium acetate, 1-ethyl-3- (2-ethylhexyl) imidazolium, 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-dioctadecyl imidazolium acetate, 1-benzyl-3-octadecylimidazolium acetate, and 1, 3-dibenzylimidazolium acetate;

1, 3-dimethylimidazolium lactate, 1-ethyl-3-methylimidazolium lactate, 1-butyl-3-methylimidazolium lactate, 1-methyl-3-octylimidazolium lactate, 1-methyl-3- (2-ethylhexyl) imidazolium lactate, 1-dodecyl-3-methylimidazolium lactate, 1-methyl-3-octadecylimidazolium lactate, 1-benzyl-3-methylimidazolium lactate, 1, 3-dibutylimidazolium lactate, 1-butyl-3-ethylimidazolium lactate, 1-butyl-3-octylimidazolium lactate, 1-butyl-3- (2-ethylhexyl) imidazolium lactate, 1-butyl-3-methylimidazolium lactate, 1-butyl-3- (2-ethylhexyl) imidazolium lactate, and mixtures thereof, 1-butyl-3-dodecylimidazolium lactate, 1-butyl-3-octadecylimidazolium lactate, 1-benzyl-3-butylimidazolium lactate, 1, 3-dioctylimidazolium lactate, 1-ethyl-3-octylimidazolium lactate, 1-octyl-3- (2-ethylhexyl) imidazolium lactate, 1-dodecyl-3-octylimidazolium lactate, 1-octyl-3-octadecylimidazolium lactate, 1-benzyl-3-octylimidazolium lactate, 1, 3-bis (2-ethylhexyl) imidazolium lactate, 1-ethyl-3- (2-ethylhexyl) imidazolium lactate, 1- (2-ethylhexyl) -3-dodecylimidazolium lactate, 1- (2-ethylhexyl) -3-octadecylimidazolium lactate, 1-benzyl-3- (2-ethylhexyl) imidazolium lactate, 1, 3-didodecylimidazolium lactate, 1-dodecyl-3-octadecylimidazolium lactate, 1-benzyl-3-dodecylimidazolium lactate, 1, 3-dioctadecyl imidazolium lactate, 1-benzyl-3-octadecylimidazolium lactate, and 1, 3-dibenzylimidazolium lactate;

1, 3-dimethylimidazolium bicarbonate, 1-ethyl-3-methylimidazolium bicarbonate, 1-butyl-3-methylimidazolium bicarbonate, 1-methyl-3-octylimidazolium bicarbonate, 1-methyl-3- (2-ethylhexyl) imidazolium bicarbonate, 1-dodecyl-3-methylimidazolium bicarbonate, 1-methyl-3-octadecylimidazolium bicarbonate, 1-benzyl-3-methylimidazolium bicarbonate, 1, 3-dibutylimidazolium bicarbonate, 1-butyl-3-ethylimidazolium bicarbonate, 1-butyl-3-octylimidazolium bicarbonate, 1-butyl-3- (2-ethylhexyl) imidazolium bicarbonate, 1-butyl-3-dodecylimidazolium bicarbonate, 1-butyl-3-octadecylimidazolium bicarbonate, 1-benzyl-3-butylimidazolium bicarbonate, 1, 3-dioctylimidazolium bicarbonate, 1-ethyl-3-octylimidazolium bicarbonate, 1-octyl-3- (2-ethylhexyl) imidazolium bicarbonate, 1-dodecyl-3-octylimidazolium bicarbonate, 1-octyl-3-octadecylimidazolium bicarbonate, 1-benzyl-3-octylimidazolium bicarbonate, 1, 3-bis (2-ethylhexyl) imidazolium bicarbonate, 1-ethyl-3- (2-ethylhexyl) imidazolium bicarbonate, 1-butyl-3-octadecylium bicarbonate, 1-octyl-imidazolium bicarbonate, 1-octyl-3-ethylhexylimidazolium bicarbonate, 1-ethyl-3- (2-ethylhexyl) imidazolium bicarbonate, 1-butyl-3-, l- (2-ethylhexyl) -3-dodecylimidazolium bicarbonate, 1- (2-ethylhexyl) -3-octadecylimidazolium bicarbonate, 1-benzyl-3- (2-ethylhexyl) imidazolium bicarbonate, 1, 3-didodecylimidazolium bicarbonate, 1-dodecyl-3-octadecylimidazolium bicarbonate, 1-benzyl-3-dodecylimidazolium bicarbonate, 1, 3-dioctadecylimidazolium bicarbonate, 1-benzyl-3-octadecylimidazolium bicarbonate, and 1, 3-dibenzylimidazolium bicarbonate;

1, 3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolium chloride, 1-methyl-3- (2-ethylhexyl) imidazolium chloride, 1-dodecyl-3-methylimidazolium chloride, 1-methyl-3-octadecylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1, 3-dibutylimidazolium chloride, 1-butyl-3-ethylimidazolium chloride, 1-butyl-3-octylimidazolium chloride, 1-butyl-3- (2-ethylhexyl) imidazolium chloride, and mixtures thereof, 1-butyl-3-dodecylimidazolium chloride, 1-butyl-3-octadecylimidazolium chloride, 1-benzyl-3-butylimidazolium chloride, 1, 3-dioctylimidazolium chloride, 1-ethyl-3-octylimidazolium chloride, 1-octyl-3- (2-ethylhexyl) imidazolium chloride, 1-dodecyl-3-octylimidazolium chloride, 1-octyl-3-octadecylimidazolium chloride, 1-benzyl-3-octylimidazolium chloride, 1, 3-bis (2-ethylhexyl) imidazolium chloride, 1-ethyl-3- (2-ethylhexyl) imidazolium chloride, 1- (2-ethylhexyl) -3-dodecylimidazolium chloride, 1-butyl-3-octadecylimidazolium chloride, 1- (2-ethylhexyl) -3-octadecylimidazolium chloride, 1-benzyl-3- (2-ethylhexyl) imidazolium chloride, 1, 3-didodecylimidazolium chloride, 1-dodecyl-3-octadecylimidazolium chloride, 1-benzyl-3-dodecylimidazolium chloride, 1, 3-dioctadecylimidazolium chloride, 1-benzyl-3-octadecylimidazolium chloride, 1, 3-dibenzylimidazolium chloride;

1, 3-dimethylimidazolinium formate, 1, 3-dimethylimidazolinium acetate, 1, 3-dimethylimidazolinium lactate, 1, 3-dimethylimidazolinium bicarbonate, 1, 3-dimethylimidazolinium chloride, 1-butyl-3-methylimidazolium formate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium lactate, 1-butyl-3-methylimidazolium bicarbonate, 1-butyl-3-methylimidazolium chloride, 1-methyl-3-octylimidazolinium formate, 1-methyl-3-octylimidazolinium acetate, 1-methyl-3-octylimidazolinium lactate, 1-methyl-3-octylimidazolinium hydrogen carbonate, 1-methyl-3-octylimidazolinium chloride; and

1, 3-dimethylbenzylimidazolium formate, 1, 3-dimethylbenzylimidazolium acetate, 1, 3-dimethylbenzylimidazolium lactate, 1, 3-dimethylbenzylimidazolium bicarbonate, 1, 3-dimethylbenzylimidazolium chloride, and the like.

Preferably 1, 3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-methyl-3-octylimidazolium 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- (2-ethylhexyl) imidazolium acetate, 1-butyl-3-octylimidazolium acetate, 1-butyl-3- (2, 1-butyl-3-dodecylimidazolium acetate, 1-butyl-3-octadecylimidazolium acetate, 1-benzyl-3-butylimidazolium acetate, 1, 3-dioctylimidazolium acetate, 1-ethyl-3-octylimidazolium acetate, 1-octyl-3- (2-ethylhexyl) imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-octyl-3-octadecylimidazolium acetate, 1-benzyl-3-octylimidazolium acetate, 1, 3-bis (2-ethylhexyl) imidazolium acetate, 1-ethyl-3- (2-ethylhexyl) imidazolium acetate, 1-benzyl-3-octylimidazolium acetate, 1-ethyl-3- (2-ethylhexyl) imidazolium, 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-dioctadecyl imidazolium acetate, 1-benzyl-3-octadecylimidazolium acetate, and 1, 3-dibenzylimidazolium acetate.

The iminium salt (1) may be a commercially available one. As the iminium salt (1), those obtained by a known method can be used, and those obtained by the following methods can be used.

For example, in the case where D is a nitrogen-containing organic group represented by the formula (2-1) in the iminium salt (1), it is preferably produced by the method described below.

A dicarbonyl compound represented by the following formula (6), a primary amine compound represented by the following formula (7a) and the following formula (7b), formaldehyde, and an acid represented by the following formula (8) are reacted with each other.

Formula (6):

[ solution 23]

In the formula (6), R⁹And R¹⁰As described above.

Formula (7 a):

[ solution 24]

R¹-NH₂ (7a)

In the formula (7a), R¹As described above.

Formula (7 b):

[ solution 25]

R⁴-NH₂ (7b)

In the formula (7b), R⁴As described above.

Formula (8):

[ solution 26]

G^-H⁺ (8)

In the formula (8), G^-As described above.

In the formula (6), R⁹And R¹⁰As described above.

Examples of the dicarbonyl compound represented by formula (6) (hereinafter referred to as dicarbonyl compound (6)) include: 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, preferably glyoxal and diacetyl, more preferably glyoxal.

In the formula (7a), R¹As described above.

In the formula (7b), R⁴As described above.

The primary amine compound represented by the formula (7a) (hereinafter referred to as primary amine compound (7a)) and the primary amine compound represented by the formula (7b) (hereinafter referred to as primary amine compound (7b)) are at least one primary amine compound selected from the group consisting of methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, hexylamine, octylamine, 2-ethylhexylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, allylamine, benzylamine, aniline, 2, 6-diisopropylaniline, and 2,4, 6-trimethylaniline, preferably methylamine, ethylamine, butylamine, hexylamine, octylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, and benzylamine, more preferably butylamine, octylamine, 2-ethylhexylamine, and benzylamine.

In the formula (8), G^-As described above.

Examples of the acid represented by formula (8) (hereinafter referred to as acid (8)) include: formic acid, acetic acid, propionic acid, butyric acid, ethoxyacetic acid, propoxyacetic acid, 2- (2-methoxyethoxy) acetic acid, 2- (2-ethoxyethoxy) acetic acid, 2- (2-propoxyethoxy) acetic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3- (2-methoxyethoxy) propionic acid, 3- (2-ethoxyethoxy) propionic acid, carboxylic acids such as 3- (2-propoxyethoxy) propionic acid, 3- (3-methoxypropoxy) propionic acid, 3- (3-ethoxypropoxy) propionic acid, 3- (3-propoxypropoxy) propionic acid, oleic acid, linoleic acid, sorbic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, salicylic acid, and trifluoroacetic acid; hydrogen halides such as hydrogen chloride, hydrogen bromide, and hydrogen iodide; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; and phosphoric acids such as dimethyl phosphoric acid, diethyl phosphoric acid, and dibutyl phosphoric acid, preferably carboxylic acids, and more preferably acetic acid.

The dicarbonyl compound (6) may be used as it is in an aqueous solution or in an alcohol solution such as methanol or butanol.

The amount of the primary amine compound (7a) and the primary amine compound (7b) used is usually 0.1 to 10 moles, preferably 0.5 to 3 moles, of the total amount of the primary amine compound (7a) and the primary amine compound (7b) based on 1 mole of the dicarbonyl compound (6).

The ratio of the primary amine compound (7a) to the primary amine compound (7b) is not particularly limited, and the primary amine compound (7 a): primary amine compound (7b) ═ 0: 100-100: the range of 0.

The formaldehyde can be used directly in the form of aqueous solution or alcoholic solution such as methanol and butanol. The amount of formaldehyde used is usually 0.1 to 10 moles, preferably 0.5 to 5.0 moles, based on 1 mole of the dicarbonyl compound (6).

The amount of the acid (8) used is usually 0.1 to 10 moles, preferably 0.5 to 2 moles, based on 1 mole of the dicarbonyl compound (6).

The optimum temperature for the reaction varies depending on the starting materials and the solvent used, but is usually-10 ℃ or higher, preferably 0 to 100 ℃.

The solvent may or may not be used. When a solvent is used, the solvent to be used is not particularly limited as long as it does not affect the reaction. Specific examples of the solvent include: aromatic hydrocarbon solvents such as toluene, benzene, and xylene; hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane, octane, and the like; halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as diethyl ether, tetrahydrofuran, and 1, 4-dioxane; alcohol solvents such as methanol and ethanol; n, N-dimethylformamide, acetonitrile, water and the like, preferably an aromatic hydrocarbon solvent, an alcohol solvent and a water solvent, and particularly preferably toluene and water. Two or more solvents may be mixed and used as necessary.

The amount of the solvent used is usually 50 parts by weight or less, preferably 0.1 to 10 parts by weight, based on 1 part by weight of the dicarbonyl compound (6).

If necessary, the reaction may be carried out in an inert gas atmosphere such as nitrogen, argon or helium which does not affect the reaction.

After the reaction is completed, the iminium salt (1) can be isolated by removing impurities (for example, unreacted raw materials) by washing with an organic solvent, concentrating the reaction solution, or the like, and if necessary, purification such as recrystallization can be performed.

G of the iminium salt (1) obtained when the reaction is carried out^-If the anion is not the target anion, the anion may be converted to the desired anion by an ion exchange reaction as required.

An organic compound represented by formula (3) (hereinafter referred to as organic compound (3)) will be described.

In the formula (3), A is 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.

When A is a substituted hydrocarbon group, examples of the substituent include: halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, alkylamino groups such as methylamino groups, dialkylamino groups such as dimethylamino groups, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as benzyloxy groups, haloalkyl groups such as trifluoromethyl groups, nitro groups, cyano groups, sulfonyl groups, (alkylamino) carbonylamino groups, (dialkylamino) carbonylamino groups, and isocyanate groups. The A hydrocarbon group may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, or the like. When the A hydrocarbon group is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom or the like, the hydrocarbon group has a group such as-O-, -NH-, -S-, etc., and the hydrocarbon chain is interrupted by these groups.

Examples of the alkyl moiety of the above alkylamino group, dialkylamino group, alkoxy group, haloalkyl group, (alkylamino) carbonylamino group, and (dialkylamino) carbonylamino group include: a straight-chain or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. The number of carbon atoms of the alkyl group is preferably 1 to 3, more preferably 1 or 2.

Examples of the aryl moiety of the aryloxy group include: an aryl group having 6 to 10 carbon atoms. Specific examples thereof include phenyl and naphthyl groups.

The number of substituents may be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

In the formula (3), n is an integer of 1 or more, preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2.

In the formula (3), Q is-NCO group or-NHCO₂R⁷And (4) a base. R⁷The hydrocarbon group may contain a hetero atom, preferably a hydrocarbon group of 1 to 50 carbon atoms that may contain a hetero atom, more preferably a hydrocarbon group of 1 to 30 carbon atoms, and particularly preferably a hydrocarbon group of 1 to 8 carbon atoms. Examples of the hydrocarbon group which may contain a hetero atom include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, allyl, benzyl, cyclohexyl, adamantyl, phenyl, 2, 6-diisopropylphenyl, 2,4, 6-trimethylphenyl, 2-methoxyethyl, 2-ethoxyethyl, and 2- (dimethylamino) ethyl, and the like. Methyl, ethyl, propyl, isopropyl, tert-butyl, octyl, cyclopentyl, cyclohexyl, 2,4, 6-trimethylphenyl are preferred, methyl, ethyl, isopropyl, tert-butyl, octyl, and phenyl are more preferred, and methyl, isopropyl, tert-butyl, octyl, and phenyl are particularly preferred.

In the present invention, the organic compound (3) is preferably an organic compound represented by any one of the formulae (3-1), (3-2) and (3-3), and particularly preferably an organic compound represented by the formula (3-1).

Formula (3-1):

[ solution 27]

R⁵-Q (3-1)

In the formula (3-1), Q is the same as above, R⁵Is a substituted or unsubstituted hydrocarbyl group.

Formula (3-2):

[ solution 28]

Q-R⁶-Q (3-2)

In the formula (3-2), Q is the same as above, R⁶Is a warpSubstituted or unsubstituted hydrocarbyl.

Formula (3-3):

[ solution 29]

In the formula (3-3), Q is the same as above, E¹、E²And E³Each independently represents a substituted or unsubstituted hydrocarbon group, or a halogen atom, alkylamino group, dialkylamino group, alkoxy group, aryloxy group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, or isocyanate group. f and g each independently represent an integer of 0 to 4. a and b are 0 or 1, and c, d and e each independently represent an integer of 0 to 4. Wherein, when f is 0, at least one of a and b is 1.

When Q is an-NCO group, the organic compound (3) is an isocyanate compound represented by the following formula (3a) (hereinafter referred to as isocyanate compound (3a)), and when Q is-NHCO₂R⁷In the case of (c), the organic compound (3) is a carbamate compound represented by the following formula (3b) (hereinafter referred to as carbamate compound (3 b)).

Formula (3 a):

[ solution 30]

In the formula (3a), A, n is the same as described above.

Formula (3 b):

[ solution 31]

In the formula (3b), A, n and R⁷As described above.

In the formulae (3-1), (3-2) and (3-3), when Q is an-NCO group, the organic compounds represented by the formulae (3-1), (3-2) and (3-3) have the structures represented by the formulae (3a-l), (3a-2) and (3a-3), respectively.

Formula (3 a-l):

[ solution 32]

R⁵-NCO (3a-1)

In the formula (3a-l), R⁵As described above.

Formula (3 a-2):

[ solution 33]

OCN-R⁶-NOC (3a-2)

In the formula (3a-2), R⁶As described above.

Formula (3 a-3):

[ chemical 34]

In the formula (3a-3), E¹、E²、E³A, b, c, d, e, f, g are the same as above.

In the present invention, as the isocyanate compound (3a), a polymer such as polymethylene polyphenyl polyisocyanate (polymeric mdi) can be used.

In the formula (3a-l), R⁵The substituted or unsubstituted hydrocarbon group is preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms. Specifically, there may be mentioned: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, dodecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl, tolyl, allyl and the like, preferably benzyl and phenyl.

When R is⁵When having a substituent, examples of the substituent include: halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkylamino groups such as methylamino group, dialkylamino groups such as dimethylamino group, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as benzyloxy group, haloalkyl groups such as trifluoromethyl group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group, and (dialkylamino) carbonylamino groupOr an isocyanate group, and the like. Furthermore, R⁵The hydrocarbon group may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. When the hydrocarbon group is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom or the like, the hydrocarbon group has a group such as-O-, -NH-, -S-, and the like, and the hydrocarbon chain is interrupted by these groups.

Examples of the alkyl moiety of the above alkylamino group, dialkylamino group, alkoxy group, haloalkyl group, (alkylamino) carbonylamino group, and (dialkylamino) carbonylamino group include: a straight-chain or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. The number of carbon atoms of the alkyl group is preferably 1 to 3, and more preferably 1 or 2.

Examples of the aryl moiety of the aryloxy group include: an aryl group having 6 to 10 carbon atoms. Specifically, there may be mentioned: phenyl, naphthyl, and the like.

The number of substituents may be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

In the formula (3a-2), R⁶The substituted or unsubstituted hydrocarbon group is 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. Specifically, there may be mentioned: alkylene groups such as methylene, dimethylmethylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, n-octadecylene, and cyclohexylene, arylene groups such as phenylene, 2-methylphenylene, 2, 6-dimethylphenylene, 2, 4-dimethylphenylene, 2, 3-dimethylphenylene, and naphthylene, arylalkylene groups such as phenylmethylene, phenylethylene, 1-phenylpropylene, 2-phenylpropylene, 1-phenylbutylene, 2-phenylbutylene, naphthylmethylene, and naphthylethylene, and arylalkylene groups in which the above alkylene groups and arylene groups are appropriately combined. These divalent hydrocarbon groups may be repeated or combined to constitute a divalent hydrocarbon group.

When R is⁶Having substituents, as substituentsExamples are: halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, alkylamino groups such as methylamino groups, dialkylamino groups such as dimethylamino groups, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as benzyloxy groups, haloalkyl groups such as trifluoromethyl groups, nitro groups, cyano groups, sulfonyl groups, (alkylamino) carbonylamino groups, (dialkylamino) carbonylamino groups, and isocyanate groups. Furthermore, R⁵The hydrocarbon group may be substituted with a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. When the hydrocarbon group is substituted with a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom or the like, the hydrocarbon group has a group such as-O-, -NH-, -S-, etc., and the hydrocarbon chain is interrupted by these groups.

Examples of the alkyl moiety of the above alkylamino group, dialkylamino group, alkoxy group, haloalkyl group, (alkylamino) carbonylamino group, and (dialkylamino) carbonylamino group include: a straight-chain or branched alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, or a pentyl group. The number of carbon atoms of the alkyl group is preferably 1 to 3, and more preferably 1 or 2.

Examples of the aryl moiety of the aryloxy group include: an aryl group having 6 to 10 carbon atoms. Specifically, there may be mentioned: phenyl, naphthyl, and the like.

The number of substituents may be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

In the formula (3a-3), E¹、E²And E³Each independently represents a substituted or unsubstituted hydrocarbon group, or a halogen atom, alkylamino group, dialkylamino group, alkoxy group, aryloxy group, nitro group, cyano group, sulfonyl group, (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, or isocyanate group, preferably a substituted or unsubstituted hydrocarbon group, (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group, or isocyanate group, more preferably (alkylamino) carbonylamino group, (dialkylamino) carbonylamino group.

f and g each independently represent an integer of 0 to 4. a and b are 0 or 1, and c, d and e each independently represent an integer of 0 to 4. Wherein, when f is 0, at least one of a and b is 1.

Herein, when the formula isR in (3a-l) and (3a-2)⁵Or R⁶When a compound having a hydrocarbon group having a (alkylamino) carbonylamino group or a (dialkylamino) carbonylamino group is used as the isocyanate compound (3a), for example, a part of isocyanate groups of an isocyanate compound having a plurality of isocyanate groups as represented by the formula (3a-2) or the formula (3a-3) may be reacted with a primary amine compound, a secondary amine compound, or the like to form a (alkylamino) carbonylamino group or a (dialkylamino) carbonylamino group, which may be used as the isocyanate compound (3 a).

When E in the formula (3a-3)¹、E²、E³In the case of the (alkylamino) carbonylamino group or the (dialkylamino) carbonylamino group, for example, a part of isocyanate groups of a polymer such as polymethylene polyphenyl polyisocyanate may be reacted with a primary amine compound or a secondary amine compound to form an (alkylamino) carbonylamino group or a (dialkylamino) carbonylamino group, which may be used as the isocyanate compound (3 a).

Examples of the primary amine compound include: methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine, octylamine, decylamine, dodecylamine, and 2-ethylhexylamine, and the like, preferably butylamine and 2-ethylhexylamine. Examples of the secondary amine compound include: dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di (sec-butyl) amine, di (tert-butyl) amine, dipentylamine, dihexylamine, dioctylamine, didecylamine, methylethylamine, didodecylamine, and di (2-ethylhexyl) amine, etc., preferably dibutylamine and di (2-ethylhexyl) amine.

Specific examples of the isocyanate compound (3a) are shown below. But the invention is not limited thereto. In the following specific examples, Et represents an ethyl group, Pr represents an n-propyl group, and Bu represents an n-butyl group.

[ solution 35]

[ solution 36]

[ solution 37]

[ solution 38]

The isocyanate compound (3a) is preferably a compound represented by the formulae (3a-l-5), (3a-l-15), (3a-l-38) and (3a-2-19), and particularly preferably a compound represented by the formula (3 a-l-15).

The isocyanate compound (3a) may be a single compound or a mixture of two or more compounds.

When Q is-NHCO in the formulae (3-1), (3-2) and (3-3)₂R⁷When the group is represented by the formula (3-1), (3-2) and (3-3), the organic compounds represented by the formulae (3b-l), (3b-2) and (3b-3) will be represented by the formulae, respectively.

Formula (3 b-l):

[ solution 39]

In the formula (3b-l), R⁵、R⁷As described above.

Formula (3 b-2):

[ solution 40]

In the formula (3b-2), R⁶、R⁷As described above.

Formula (3 b-3):

[ solution 41]

In the formula (3b-3), R⁷、E¹、E²、E³A, b, c, d, e, f, g are the same as above.

In the formula (3b-1), R⁵、R⁷As described above.

In the formula (3b-2), R⁶、R⁷As described above.

In the formula (3b-3), R⁷、E¹、E²、E³A, b, c, d, e, f, g are the same as above.

Specific examples of the urethane compound (3b) are shown below. But the invention is not limited thereto. In the following specific examples, Et represents an ethyl group, Pr represents an n-propyl group, and Bu represents an n-butyl group.

[ solution 42]

[ solution 43]

[ solution 44]

As the urethane compound (3b), preferred are those of the formulae (3b-1-15p), (3b-1-15q), (3b-1-21p), (3b-1-21q), (3b-1-28p), (3b-1-28q), (3b-1-32p), (3b-1-32q), (3b-1-33p), (3b-1-33q), (3b-1-34p), (3b-1-34q), (3b-1-38p), (3b-1-38q), (3b-1-43p), (3b-1-43q), (3b-1-48p), The compound represented by (3b-1-48q), (3b-1-49p), (3b-1-49q), (3b-1-50p), (3b-1-50q), (3b-2-12p), (3b-2-12q), (3b-2-14p), (3b-2-14q), (3b-2-15p), (3b-2-15q), (3b-2-16p), (3b-2-16q), (3b-2-18p), or (3b-2-18q), and the compound represented by the formula (3b-l-15p) is particularly preferable.

The urethane compound (3b) used as a raw material can be produced by a known method using a commercially available product.

An amide-based compound represented by the formula (4) (hereinafter referred to as the amide-based compound (4)) will be described.

In formula (4), A, D and n are the same as described above.

The amide-based compound (4) is preferably an amide-based compound represented by any one of the formulae (4-1), (4-2) and (4-3), and particularly preferably an amide-based compound represented by the formula (4-1).

Formula (4-1):

[ solution 45]

In the formula (4-1), R⁵And D are the same as above.

Formula (4-2):

[ solution 46]

In the formula (4-2), R⁶And D are the same as above.

Formula (4-3):

[ solution 47]

In the formula (4-3), D, E¹、E²、E³A, b, c, d, e, f and g are the same as described above.

In the formula (4-1), R⁵And D are the same as above.

In the formula (4-2), R⁶And D are the same as above.

In the formula (4-3), D, E¹、E²、E³A, b, c, d, e, f and g are the same as described above.

Next, specific examples of the amide-based compound (4) are shown. But the invention is not limited thereto. In the following specific examples, Et represents an ethyl group, Pr represents an n-propyl group, and Bu represents an n-butyl group.

[ solution 48]

[ solution 49]

[ solution 50]

[ solution 51]

[ solution 52]

[ Hua 53]

[ solution 54]

[ solution 55]

In the formulas (4-3-1r) - (4-3-1v), m is an integer of 0-4.

[ solution 56]

In the formulae (4-3-2r) to (4-3-2v), (4-3-3r) to (4-3-3v) and (4-3-4r) to (4-3-4v), x and y are integers of 0 or 1 or more.

The amide-based compound (4) is preferably represented by the formula (4-1-5r), (4-1-15r), (4-1-16r), (4-1-18r), (4-1-19r), (4-1-21r), (4-1-24r), (4-1-26r), (4-1-27r), (4-1-28r), (4-1-5s), (4-1-15s), (4-1-16s), (4-1-18s), (4-1-19s), (4-1-21s), (4-1-24s), (4-1-26s), (4-1-27s), (4-1-28s), (4-1-5t), (4-1-15t), (4-1-16t), (4-1-18t), (4-1-19t), (4-1-21t), (4-1-24t), (4-1-26t), (4-1-27t), (4-1-28t), (4-1-5u), (4-1-15u), (4-1-16u), (4-1-18u), (4-1-19u), (4-1-21u), (4-1-24u), (4-1-26u), (4-1-27u), (4-1-28u), (4-1-5v), (4-1-15v), (4-1-16v), (4-1-18v), (4-1-19v), (4-1-21v), (4-1-24v), (4-1-26v), (4-1-27v), (4-1-28v), (4-2-13r), (4-2-14r), (4-2-19r), (4-2-21r), (4-2-22r), (4-2-23r), (4-2-25r), (4-2-13s), (4-2-14s), (4-2-19s), (4-2-21s), (4-2-22s), (4-2-23s), (4-2-25s), (4-2-13t), (4-2-14t), (4-2-19t), (4-2-21t), (4-2-22t), (4-2-23t), (4-2-25t), (4-2-13u), (4-2-14u), (4-2-19u), (4-2-21u), (4-2-22u), (4-2-23u), (4-2-25u), (4-2-13v), The compounds represented by (4-2-14v), (4-2-19v), (4-2-21v), (4-2-22v), (4-2-23v) and (4-2-25v) are particularly preferably compounds represented by the formulae (4-l-15r), (4-1-15s), (4-l-15t), (4-l-15u) and (4-l-15 v).

When the amide-based compound (4) has isomers such as optical isomers, stereoisomers, and positional isomers, a mixture of any isomer is included in the amide-based compound (4) unless it is specified which isomer is. For example, when the amide-based compound (4) has optical isomers, the optical isomers thereof resolved from the racemate may be contained in the amide-based compound (4). These isomers can be obtained as single compounds by conventionally known separation techniques (concentration, solvent extraction, column chromatography, recrystallization, etc.).

The reaction of the iminium salt (1) with the organic compound (3) will be described.

In the reaction of the iminium salt (1) with the organic compound (3), the reaction is usually carried out in such an amount that the iminium salt (1) is 0.8 mol or more, preferably 1 to 3mol, relative to 1mol of the group represented by Q contained in the organic compound (3).

The reaction temperature is not particularly limited, but is generally-10 ℃ or higher, preferably 0 to 200 ℃, and more preferably 20 to 150 ℃.

The solvent may or may not be used. Examples of the solvent include: aromatic hydrocarbon solvents such as toluene, benzene and xylene, aliphatic hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane and octane, halogenated hydrocarbon solvents such as chlorobutane and 1, 2-dichloroethane, halogenated aromatic hydrocarbon solvents such as chlorobenzene, etc., preferably aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, and particularly preferably toluene, xylene and chlorobenzene. Two or more solvents may be used in combination as necessary.

The amount of the solvent used is usually 50 parts by weight or less, preferably 0.1 part by weight or more and 35 parts by weight or less, based on 1 part by weight of the iminium salt (1).

If necessary, the reaction may be carried out in an inert gas atmosphere such as nitrogen, argon or helium which does not affect the reaction.

After the reaction is completed, the solvent may be removed by concentration or filtration of the reaction solution to obtain the amide-based compound (4), and purification such as recrystallization or column fractionation may be performed as necessary.

< blocking agent cleavage catalyst for blocked isocyanate >

The amide-based compound (4) can be used as a blocking agent dissociation catalyst for blocked isocyanates. The blocking agent dissociation catalyst for blocked isocyanate means a catalyst that can promote a reaction for dissociating a blocking agent that blocks an isocyanate group of blocked isocyanate to suppress the reaction.

When the amide-based compound (4) is used as a blocking agent dissociation catalyst for blocked isocyanate, the amide-based compound (4) is preferably an amide-based compound (4) having a nitrogen-containing organic group as the nitrogen-containing organic group, wherein R in formula (2) is R, from the viewpoint of improving compatibility with urethane resin with respect to a mixture of the blocked isocyanate and a compound having an isocyanate-reactive group¹And R⁴The same or different, is a hydrocarbon group of 2-30 carbon atoms which may contain hetero atoms; more preferably an amide-based compound (4) having a nitrogen-containing organic group as the nitrogen-containing organic group, R¹And R⁴The same or different, and is a hydrocarbon group of 7 to 30 carbon atoms which may contain a hetero atom; more preferably still, the amide-based compound (4) having a nitrogen-containing organic group as the nitrogen-containing organic group R¹And R⁴The same or different hydrocarbon groups may contain hetero atoms and have 7 to 20 carbon atoms.

A blocking agent dissociation catalyst for blocked isocyanate (hereinafter referred to as blocking agent dissociation catalyst (a)) containing the amide-based compound (4) will be described.

The blocking agent dissociation catalyst (a) may be used alone or in the form of a mixture of two or more. Further, a solvent may be mixed and used as necessary.

The solvent is not particularly limited, and examples thereof include: a hydrocarbon solvent such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha, a ketone solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, an ester solvent such as ethyl acetate, butyl acetate, and cellosolve acetate, an alcohol solvent such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol, a polyol solvent such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin, and water.

The blocking agent dissociation catalyst (A) for blocked isocyanate of the present invention is a catalyst that promotes dissociation of a blocking agent for blocked isocyanate; and a catalyst for curing a mixture of a blocked isocyanate and a compound having an isocyanate-reactive group.

The blocking agent dissociation catalyst (a) of the present invention can sufficiently achieve the object of the present invention as long as it contains the amide-based compound (4) as an active ingredient, and may contain a known blocking agent dissociation catalyst for blocked isocyanate as needed.

The present invention also includes the following aspects.

An amide-based compound represented by the above formula (4) which is used as a blocking agent dissociation catalyst for blocked isocyanates.

Use of the amide-based compound represented by the above formula (4) as a cleavage catalyst for a blocking agent for blocked isocyanates.

The use of the amide-based compound represented by the formula (4) for producing a blocking agent dissociation catalyst for blocked isocyanates.

The blocking agent dissociation catalyst of the blocking agent of the present invention can be suitably used as a catalyst for a blocking agent dissociation method, for example.

In the method of the present invention, the blocked isocyanate is heated in the presence of the blocking agent dissociation catalyst for blocked isocyanate.

In the method of the present invention, the amount of the blocking agent dissociation catalyst (a) used is not particularly limited, and in the thermosetting composition described below, the amount of the amide-based compound (4) contained in the blocking agent dissociation catalyst (a) is usually 0.01 to 15% by weight, preferably 0.05 to 10% by weight, and more preferably 0.1 to 5% by weight.

The reaction temperature may be about 60 to 250 ℃ depending on the blocked isocyanate used, and preferably about 80 to 200 ℃. The reaction time is about 30 seconds to 5 hours, preferably about 30 seconds to 2 hours.

Blocking by the blocking agent can be released by the process of the invention.

Next, the thermosetting composition of the present invention will be described.

The thermosetting composition of the present invention contains the blocking agent dissociation catalyst (a) of the present invention, a blocked isocyanate, and a compound having an isocyanate-reactive group.

Examples of the blocked isocyanate include: a compound obtained by reacting a known polyisocyanate with a known blocking agent to block an isocyanate group in the polyisocyanate with the blocking agent. The blocked isocyanate may be one kind alone or two or more kinds thereof may be mixed.

In the present invention, the polyisocyanate is not particularly limited as long as it is a compound having 2 or more isocyanate groups, and known polyisocyanates include: aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic aliphatic polyisocyanate, modified polyisocyanate thereof, and the like. These polyisocyanates may be used alone or in combination of two or more.

Examples of the aliphatic polyisocyanate include: 1, 4-tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include: 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3, 3, 5-trimethylcyclohexane (isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane, norbornane diisocyanate, and the like.

Examples of the aromatic polyisocyanate include: 2,4 '-diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 3 '-dimethyl-4, 4' -diisocyanatodiphenyl, 3 '-dimethyl-4, 4' -diisocyanatodiphenylmethane, 1, 5-naphthalene diisocyanate, and the like.

Examples of the aromatic aliphatic polyisocyanate include: 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, and α, α, α ', α' -tetramethylxylylene diisocyanate.

Examples of the modified polyisocyanate include: an isocyanate group-terminated compound formed by reacting the polyisocyanate compound with a compound having an active hydrogen group, a polyisocyanate compound, and/or a reaction product of the isocyanate group-terminated compound (for example, an adduct type polyisocyanate, an isocyanate-modified product obtained by allophanatization, carbodiimidization, uretdionization, isocyanurateation, uretoniuretonimization, or biuretization).

Examples of known blocking agents include: alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, 2-ethylhexanol, and butyl cellosolve; phenols such as phenol, cresol and 2-hydroxypyridine, and amines such as diisopropylamine; lactams such as epsilon-caprolactam, delta-valerolactam and gamma-butyrolactam; oximes such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and the like; ketoenols such as acetylacetone; pyrazoles such as 1, 2-pyrazole and 3, 5-dimethylpyrazole; and triazoles such as triazole, preferably lactams, oximes, pyrazoles, and particularly preferably epsilon-caprolactam, methyl ethyl ketoxime, and 3, 5-dimethylpyrazole.

Examples of the compound having an isocyanate reactive group include: and compounds having 2 or more active hydrogen groups such as polyols, polyamines, and alkanolamines. These compounds having an isocyanate reactive group may be a mixture of two or more.

In the present invention, the polyol is a compound having 2 or more hydroxyl groups. Examples of the polyhydric alcohol include: polyether polyols, polyester polyols, acrylic polyols, polyolefin polyols, fluorine polyols, polycarbonate polyols, polyurethane polyols, and the like. These polyols may be a mixture of two or more.

Examples of polyether polyols include: active hydrogen compounds such as aliphatic amine polyols, aromatic amine polyols, mannich polyols, polyphenols and bisphenols, and compounds obtained by adding alkylene oxides to these compounds. These polyether polyols may be mixtures of two or more.

Examples of the aliphatic amine polyol include alkylene diamine polyols and alkanolamine polyols. These polyol compounds are hydroxyl-terminated polyfunctional polyol compounds obtained by ring-opening addition of at least one cyclic ether such as ethylene oxide or propylene oxide using an alkylenediamine or an alkanolamine as an initiator. The alkylene diamine may be any known compound without limitation. Specifically, alkylene diamines having 2 to 8 carbon atoms such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine are preferably used. Among them, alkylene diamines having a small number of carbon atoms are more preferably used, and polyol compounds using ethylene diamine and propylene diamine as initiators are particularly preferably used. As the alkanolamine, monoethanolamine, diethanolamine and triethanolamine can be exemplified. The number of functional groups of the polyol compound using an alkylenediamine as an initiator is 4, the number of functional groups of the polyol compound using an alkanolamine as an initiator is 3, and the number of functional groups of the mixture of these is 3 to 4. The hydroxyl value of the aliphatic amine polyol is usually 100 to 1500mgKOH/g, preferably 200 to 1200 mgKOH/g. These aliphatic amine polyols may be a mixture of two or more kinds.

The aromatic amine polyol is a polyfunctional polyether polyol compound having a terminal hydroxyl group, which is obtained by ring-opening addition of at least one of cyclic ethers such as ethylene oxide and propylene oxide using an aromatic diamine as an initiator. The initiator may be any known aromatic diamine. Specifically, there may be mentioned: 2, 4-tolylenediamine, 2, 6-tolylenediamine, diethyltolylenediamine, 4' -diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthylenediamine, and the like. Among them, tolylenediamine (2, 4-tolylenediamine, 2, 6-tolylenediamine, or a mixture thereof) is particularly preferably used. The aromatic amine polyol has a functional group number of 4 and a hydroxyl value of usually 100 to 1500mgKOH/g, preferably 200 to 1200 mgKOH/g. These aromatic amine polyols may be a mixture of two or more kinds.

The Mannich polyol is an active hydrogen compound obtained by Mannich reaction of phenol and/or an alkyl-substituted derivative thereof, formaldehyde and an alkanolamine, or a polyol compound having a hydroxyl value of 200 to 700mgKOH/g and a functional group number of 2 to 4 obtained by ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide to the compound. These mannich polyols may be mixtures of two or more.

Examples of the polyhydric alcohol include: dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, etc.), trihydric or higher alcohols (e.g., glycerin, trimethylolpropane, pentaerythritol, methyl glucoside, sorbitol, sucrose, etc.), and the like. These polyols may be a mixture of two or more.

Examples of the polyhydric phenol include: pyrogallol, hydroquinone, and the like. These polyhydric phenols may be a mixture of two or more kinds.

Examples of the bisphenols include: bisphenol A, bisphenol S, bisphenol F, and low condensates of phenol and formaldehyde. These bisphenols may be a mixture of two or more.

Examples of the polyester polyol include: polyester polyols obtained by the condensation reaction of a dibasic acid selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid and terephthalic acid, and a polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, glycerin, and the like, alone or in a mixture thereof; and polycaprolactones obtained by ring-opening polymerization of epsilon-caprolactone using a polyol. These polyester polyols may be a mixture of two or more.

The acrylic polyol is a compound obtained by copolymerizing: monomers containing ethylenically unsaturated bonds having hydroxyl groups (Japanese text: エチレン nature no and no arrangement), alone or in combination; and other ethylenically unsaturated bond-containing monomers copolymerizable therewith, alone or in admixture. Examples of the ethylenically unsaturated bond-containing monomer having a hydroxyl group include: hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and the like, preferably hydroxyethyl acrylate, hydroxyethyl methacrylate. These acrylic polyols may be a mixture of two or more kinds.

Examples of the other ethylenically unsaturated bond-containing monomer copolymerizable with the hydroxyl group-containing ethylenically unsaturated bond-containing monomer include: acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, benzyl methacrylate, and phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; unsaturated amides such as acrylamide, methacrylamide, N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic acid amide, and maleimide; and vinyl monomers such as glycidyl methacrylate, styrene, vinyl toluene, vinyl acetate, acrylonitrile, and dibutyl fumarate; vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane and γ - (meth) acryloyloxypropyltrimethoxysilane.

Examples of the polyolefin polyol include: polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, etc. having 2 or more hydroxyl groups. These polyolefin polyols may be a mixture of two or more.

The fluorine polyol is a polyol containing fluorine in the molecule, and examples thereof include: copolymers such as fluoroolefins, cyclic vinyl ethers, hydroxyalkyl vinyl ethers, and vinyl monocarboxylic acid esters. These fluorine polyols may be a mixture of two or more kinds.

Examples of the polycarbonate polyol include: and a low-molecular-weight carbonate compound such as dialkyl carbonate such as dimethyl carbonate, alkylene carbonate such as ethylene carbonate, and diaryl carbonate such as diphenyl carbonate, and a low-molecular-weight polyol used for the polyester polyol described above. These polycarbonate polyols may be a mixture of two or more.

The polyurethane polyol can be produced by a conventional method, for example, by reacting a polyol with a polyisocyanate. Examples of the polyol having no carboxyl group include low molecular weight substances: ethylene glycol, propylene glycol and the like, and as high molecular weight substances, there may be mentioned: acrylic polyols, polyester polyols, polyether polyols, and the like. These polyurethane polyols may be a mixture of two or more.

In the present invention, the polyamine is a compound having 2 or more amino groups. Examples of the polyamine include: low molecular weight polyamines, high molecular weight polyamines, alkanolamines, and the like. These polyamines may be a mixture of two or more.

Examples of the low-molecular-weight polyamine include: aromatic amines such as 4, 4' -diphenylmethanediamine, aromatic aliphatic amines such as 1, 3-or 1, 4-xylylenediamine or a mixture thereof, alicyclic amines such as 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine, 1, 3-bis (aminomethyl) cyclohexane and 1, 4-cyclohexanediamine, aliphatic amines such as ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 6-hexamethylenediamine, hydrazine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and the like. These low molecular weight polyamines may be a mixture of two or more.

Examples of the high-molecular-weight polyamine include: polyoxyalkylene diamine (weight average molecular weight 400-4000) and polyoxyalkylene triamine (weight average molecular weight 400-5000). These high molecular weight polyamines may be a mixture of two or more.

As the alkanolamine, for example: monoethanolamine, diethanolamine, N- (2-aminoethyl) ethanolamine, N- (2-hydroxypropyl) ethylenediamine, monopropanolamine, monoisopropanolamine, dipropanolamine, diisopropanolamine, ethyleneglycol bis (3-aminopropyl) ether, neopentanolamine, methylethanolamine, and the like.

In the thermosetting composition of the present invention, the blending ratio of the blocked isocyanate and the compound having an isocyanate-reactive group is not particularly limited, depending on the desired physical properties, and is usually within a range of [ effective isocyanate group (mol) of the blocked isocyanate ]/[ active hydrogen group (mol) of the compound having an isocyanate-reactive group) ], from 0.2 to 3. The effective isocyanate group of the blocked isocyanate means an isocyanate group regenerated when the blocking agent is dissociated from the blocked isocyanate.

In the thermosetting composition of the present invention, the amount of the blocking agent dissociation catalyst (a) of the present invention is not particularly limited, and is usually an amount such that the amount of the amide-based compound (4) contained in the blocking agent dissociation catalyst (a) in the thermosetting composition is 0.01 to 15% by weight, preferably 0.05 to 10% by weight, and more preferably 0.1 to 5% by weight.

In the thermosetting composition of the present invention, a catalyst, an additive, a pigment, a solvent, and the like, which are generally used in the art for producing polyurethane, may be used as necessary.

The catalyst for producing polyurethane is not particularly limited, and examples thereof include: tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanoate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide (Japanese text: ジブチル ジオキサイド), dioctyltin dioxide (Japanese text: ジオクチル ジオキサイド), tin bis (acetylacetonate), tin acetate, tin octylate, and tin laurate; bismuth compounds such as bismuth octoate, bismuth naphthenate and bismuth acetylacetonate; titanium compounds such as tetra-n-butyl titanate, tetra-isopropyl titanate, and titanium terephthalate; triethylamine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetramethylpropylenediamine, N, N, N ', N' -pentamethyldiethylenetriamine, 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 (DABCO), 1, 8-diazabicyclo [5.4.0] undecene-7, triethyldiamine, N, N, N ', N' -tetramethylhexamethylenediamine, N-methyl-N '- (2-dimethylaminoethyl) piperazine, N, N' -dimethylpiperazine, Quaternary ammonium salt compounds such as tertiary amine compounds such as 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, tetramethylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate and tetraalkylammonium organic acid salts such as 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

The additive is not particularly limited, and examples thereof include: hindered amine-based, benzotriazole-based, benzophenone-based ultraviolet absorbers and the like; coloring inhibitors such as perchlorate-based and hydroxylamine-based; antioxidants such as hindered phenol type, phosphorus type, sulfur type, and hydrazide type; tin-based, zinc-based, amine-based, and other urethanization catalysts; others such as leveling agents, rheology control agents, pigment dispersants, and the like.

The pigment is not particularly limited, and examples thereof include: organic pigments such as quinacridone, azo and phthalocyanine pigments; inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica; other pigments such as carbon-based pigments, metallic foil-like pigments, and rust-preventive pigments.

The solvent is not particularly limited, and examples thereof 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, cellosolve acetate, and the like; 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; water, etc., and these solvents may be used alone or in combination of two or more.

When the thermosetting composition of the present invention is stored at a high temperature, it is prepared by dividing the composition into a blocked isocyanate and a compound having an isocyanate-reactive group to prepare a two-component thermosetting composition, and the two-component thermosetting composition may be mixed to prepare the thermosetting composition of the present invention before use. In this case, the blocking agent dissociation catalyst (a) may be added to the two-pack thermosetting composition and used, or a compound having an isocyanate reactive group and the blocking agent dissociation catalyst (a) may be mixed in advance.

The thermosetting composition of the present invention is useful as a top coat/middle coat paint for automobiles, a chipping-resistant paint, an electrodeposition paint, a paint for automobile parts, a paint for automobile repair, a pre-coated/rustproof steel sheet for metal products such as home appliances and business equipment, a paint for construction materials, a paint for plastics, a powder paint, an adhesive, an adhesion-imparting agent, a sealant, etc.

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

In the method of the present invention, a mixture of the blocked isocyanate and the compound having an isocyanate-reactive group is heated in the presence of the blocking agent dissociation catalyst for blocked isocyanate described above.

The reaction temperature is also different depending on the blocked isocyanate used, but may be set to about 60 to 250 ℃, preferably about 80 to 200 ℃. The reaction time may be about 30 seconds to 5 hours, and preferably about 1 minute to 30 minutes.

Examples

The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the production example, it is noted that, in the production example,¹H-NMR was measured at 400MHz using AV400 manufactured by Bruker K.K.

< baking of thermosetting composition >

The thermosetting composition was applied to an aluminum plate (manufactured by PALTEK corporation, A5052P), and baked on a hot plate at 140 ℃ for 30 minutes.

< evaluation of compatibility >

After the baked coating film was cooled to room temperature, whether the appearance of the coating film was cloudy or transparent was visually confirmed to evaluate the compatibility.

< evaluation of solvent resistance >

The baked coating film was cooled to room temperature, and then wiped with absorbent cotton impregnated with 4-methyl-2-pentanone back and forth 10 times to observe whether or not the coating film was dissolved and exposed on an aluminum plate as a coated object, thereby evaluating the solvent resistance.

Production example 1 Synthesis of 1, 3-Dioctylimidazolium acetate ([ DOI ] [ OAc ])

[ solution 57]

77.5g (0.60mol) of octylamine was charged into a 300mL four-port reactor purged with nitrogen, and the reaction mixture was cooled to 10 ℃ or lower. Then, a mixture of 22.9g (0.30mol of pure formaldehyde) of a 40% aqueous formaldehyde solution and 27.0g (0.45mol) of acetic acid was added dropwise over 2 hours, and the mixture was stirred at 0 ℃ for 30 minutes. Then, the temperature was returned to room temperature, 43.5g of a 40% aqueous glyoxal solution (0.30mol of pure glyoxal) was added, and the resulting mixture was stirred at room temperature for 20 hours. After stirring, the resulting reaction mixture was washed 3 times with heptane 50g, and the resulting aqueous layer was concentrated under reduced pressure to obtain the compound represented by the above formula ([ DOI ]][OAc])108.4 g. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝9.32(s,1H)、7.80(s,2H)、4.17(t,J＝9.6Hz,4H)、1.78(m,4H)、1.63(s,3H)、1.23(m,20H)、0.85(t,J＝6.4Hz,6H)

Production example 2 Synthesis of 1, 3-bis (2-ethylhexyl) imidazolium acetate ([ D2EHI ] [ OAc ])

[ solution 58]

77.5g (0.60mol) of 2-ethylhexylamine was charged into a 300mL four-port reactor purged with nitrogen, and the reaction mixture was cooled to 10 ℃ or lower. Then, a mixture of 22.8g (0.30mol of pure formaldehyde) of a 40% aqueous formaldehyde solution and 27.0g (0.45mol) of acetic acid was added dropwise over 2 hours, and the mixture was stirred at 0 ℃ for 30 minutes. Then, the temperature was returned to room temperature, 43.5g of a 40% aqueous glyoxal solution (0.30mol of pure glyoxal) was added, and the resulting mixture was stirred at room temperature for 20 hours. After stirring, the resulting reaction mixture was washed 3 times with heptane 50g, and the resulting aqueous layer was concentrated under reduced pressure to obtain a compound ([ D2 EHI) represented by the above formula][OAc])98.2 g. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝9.35(s,1H)、7.82(s,2H)、4.15(d,J＝7.2Hz,4H)、1.84(m,2H)、1.71(s,3H)、1.25(m,16H)、0.87(t,J＝7.2Hz,12H)

Production example 3 Synthesis of 1, 3-dibenzylimidazolium acetate ([ DBnI ] [ OAc ])

[ chemical 59]

A300 mL four-port reactor purged with nitrogen was charged with 32.1g (0.30mol) of benzylamine, and the reaction mixture was cooled to 10 ℃ or lower. Subsequently, a mixture of 11.4g (0.15 mol of pure formaldehyde) of a 40% aqueous formaldehyde solution and 13.5g (0.22mol) of acetic acid was added dropwise over 2 hours, and the mixture was stirred at 0 ℃ for 30 minutes. Then, the mixture was returned to room temperature, 21.8g of a 40% aqueous glyoxal solution (0.15 mol of pure glyoxal), 28g of methanol and 28g of toluene were added, and the resulting mixture was stirred at room temperature for 20 hours. After stirring, the resulting reaction mixture was washed 3 times with heptane 25g, and the resulting aqueous layer was concentrated under reduced pressure to obtain a compound represented by the above formula ([ DBnI)][OAc])45.3 g. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝9.48(s,1H)、7.83(s,2H)、7.43(m,10H)、5.43(s,4H)、1.77(s,3H)

Production example 4 Synthesis of 1, 3-dibutylimidazolium acetate ([ DBI ] [ OAc ])

[ solution 60]

A300 mL four-port reactor purged with nitrogen was charged with 40.0g (0.55mol) of butylamine, and the reaction mixture was cooled to 10 ℃ or lower. Subsequently, a mixture of 20.8g (0.27 mol of pure formaldehyde) of a 40% aqueous formaldehyde solution and 24.6g (0.41mol) of acetic acid was added dropwise over 2 hours, and the mixture was stirred at 0 ℃ for 30 minutes. Then, the temperature was returned to room temperature, 39.6g of a 40% aqueous glyoxal solution (0.27 mol of pure glyoxal) was added, and the resulting mixture was stirred at room temperature for 20 hours. After stirring, the resulting reaction mixture was washed 3 times with heptane 50g, and the resulting aqueous layer was concentrated under reduced pressure to obtain a compound ([ DBI ] represented by the above formula][OAc])75.8 g. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝9.53(s,1H)、7.82(s,2H)、4.19(t,J＝6.8Hz,4H)、1.81(m,4H)、1.68(s,3H)、1.29(m,4H)、0.91(t,J＝7.2Hz,6H)

Production example 5 Synthesis of 1, 3-Dioctylimidazolium formate ([ DOI ] [ HCO2])

[ solution 61]

A300 mL four-port reactor purged with nitrogen was charged with 4.5g (0.03mol) of octylamine, and the reaction mixture was cooled to 10 ℃ or lower. Subsequently, a mixture of 1.3g (0.02 mol of pure formaldehyde) of a 40% aqueous formaldehyde solution and 1.2g (0.03mol) of formic acid was added dropwise thereto, and the mixture was stirred at 0 ℃ for 30 minutes. Then, the temperature was returned to room temperature, 2.5g of a 40% aqueous glyoxal solution (0.02 mol of pure glyoxal) was added, and the resulting mixture was stirred at room temperature for 20 hours. After stirring, the resulting reaction mixture was washed 3 times with heptane 50g, and the resulting aqueous layer was concentrated under reduced pressure to obtain the compound represented by the above formula ([ DOI ]][HCO2])6.4 g. Of a compound represented by the above formula¹H-NMR spectroscopyThe analysis results are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝9.28(s,1H)、8.43(s,1H)7.81(s,2H)、4.16(t,J＝7.2Hz,4H)、1.82-1.76(m,4H)、1.24(m,20H)、0.85(t,J＝7.2Hz,6H)

Production example 1 Synthesis of 1, 3-dioctylimidazolium-2-N-phenylamide salt (DOIm _ PI)

[ solution 62]

Charging the [ DOI ] obtained in production example 1][OAc]10.0g (0.03mol), 50.0g of chlorobenzene, and 3.0g of molecular sieve 4A3, and the mixture was allowed to stand under nitrogen for 16 hours. Then, the molecular sieve 4A was removed by filtration, and the resulting solution was charged into a 200mL three-port reactor purged with nitrogen, 15.4g (0.10mol) of methyl N-phenylcarbamate was added, and the mixture was stirred at 130 ℃ for 4 hours. After stirring, the resulting reaction mixture was concentrated under reduced pressure to obtain 24.0g of a brown solid. The resulting brown liquid was separated by an alumina column to obtain a compound (DOIm _ PI) represented by the above formula. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝7.60(s,2H)、7.41(d,J＝8.4Hz,2H)、7.12(d,J＝8.4Hz,2H)、6.79(t,J＝8.4Hz,1H)、4.48(t,J＝7.2Hz,4H)、1.79(m,4H)、1.28(m,20H)、0.87(t,J＝7.2Hz,6H)

Production example 2 Synthesis of 1, 3-bis (2-ethylhexyl) imidazolium-2-N-phenylamide salt (D2EHIm _ PI)

[ solution 63]

Was charged with [ D2HI ] obtained in production example 2][OAc]10.0g (0.03mol), 50.0g of chlorobenzene, and 3.0g of molecular sieve 4A3, and the mixture was allowed to stand under nitrogen for 16 hours. Then, the molecular sieve 4A was removed by filtration, and the resulting solution was charged into a 200mL three-port reactor purged with nitrogen, 11.8g (0.08mol) of methyl N-phenylcarbamate was added, and the mixture was stirred at 130 ℃ for 4 hours. Stirring deviceAfter stirring, 2.0g of naoh, 25.0g of meoh, and 50.0g of water were added to the obtained reaction mixture, and the organic layer was extracted. Then, 50.0g of water was added to the organic layer, and extraction was performed again. The resulting organic layer was then concentrated under reduced pressure to obtain 19.5g of a brown liquid. The resulting brown liquid was separated by an alumina column to obtain a compound (D2EHIm _ PI) represented by the above formula. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝7.59(s,2H)、7.39(d,J＝8.4Hz,2H)、7.12(t,J＝8.4Hz,2H)、6.76(t,J＝8.4Hz,1H)、4.44(t,J＝6.8Hz,4H)、1.86(m,2H)、1.25(m,16H)、0.82(m,12H)

Production example 3 Synthesis of 1, 3-dibenzylimidazolium-2-N-phenylamide salt (DBnIm _ PI)

[ solution 64]

The mixture was charged with [ DBnI ] obtained in production example 3][OAc]10.0g (0.03mol), 50.0g of chlorobenzene, and 3.0g of molecular sieve 4A3, and the mixture was allowed to stand under nitrogen for 16 hours. Then, the molecular sieve 4A was removed by filtration, and the resulting solution was charged into a 200mL three-port reactor purged with nitrogen, 11.8g (0.08mol) of methyl N-phenylcarbamate was added, and the mixture was stirred at 130 ℃ for 4 hours. After stirring, the resulting reaction mixture was concentrated under reduced pressure to obtain 21.0g of a brown liquid. The resulting brown liquid was separated by an alumina column to obtain a compound (dbnimi _ PI) represented by the above formula. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝7.65(s,2H)、7.43(m,12H)、7.12(d,J＝8.4Hz,2H)、6.83(t,J＝8.4Hz,1H)、5.83(s,4H)

Production example 4 Synthesis of 1, 3-dibutylimidazolium-2-N-phenylamide salt (DBIm _ PI)

[ solution 65]

The [ DBI ] obtained in production example 4 was charged][OAc]10.0g (0.04mol), chlorobenzene 50.0g, molecular sieve 4A0.3g, under nitrogen standing for 16 hours. Then, the molecular sieve 4A was removed by filtration, and the resulting solution was charged into a 200mL three-port reactor purged with nitrogen, 11.8g (0.08mol) of methyl N-phenylcarbamate was added, and the mixture was stirred at 130 ℃ for 4 hours. After stirring, the resulting reaction mixture was concentrated under reduced pressure to obtain 20.0g of a brown liquid. The resulting brown liquid was separated by an alumina column to obtain a compound (DBIm _ PI) represented by the above formula. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝7.60(s,2H)、7.42(d,J＝8.4Hz,2H)、7.14(d,J＝7.6Hz,2H)、6.80(t,J＝7.6Hz,1H)、4.48(t,J＝7.6Hz,4H)、1.80(m,4H)、1.30(m,4H)、0.91(t,J＝7.6Hz,6H)

Production example 5 Synthesis of DOIm _ PI

0.5g (3.2mmol) of [ DOI ] [ HCO2] obtained in production example 5, 5.3g of chlorobenzene, and 0.5g of molecular sieves 4A0.5g were charged, and the mixture was allowed to stand under nitrogen for 16 hours. Then, the molecular sieve 4A was removed by filtration, and the resulting solution was charged into a 15mL test tube purged with nitrogen, and l.g (6.9mmol) of methyl N-phenylcarbamate was added thereto, followed by stirring at 130 ℃ for 4 hours. After stirring, the resulting reaction mixture was concentrated under reduced pressure, and the resulting brown liquid was separated by means of an alumina column to obtain DOIm _ PI.

Production example 6 Synthesis of 1-ethyl-3-methylimidazolium-2-N-phenylamide salt (EMIm _ PI)

[ solution 66]

A15 mL test tube was charged with 0.9g (5.3mmol) of 1-ethyl-3-methylimidazolium acetate (Tokyo chemical industry Co., Ltd.), 3.0g (25.2mmol) of phenylisocyanate and 5.1g of chlorobenzene, and stirred at 20 ℃ for 20 minutes. After stirring, the resulting reaction mixture was concentrated under reduced pressure to obtain 0.9g of a brown liquid. The resulting brown liquid was separated by an alumina column to obtain a compound (EMIm _ PI) represented by the above formula. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(DMSO-d6)δ(ppm)＝7.61(s,1H)、7.57(s,1H)、7.46(d,J＝7.6Hz,2H)、7.27(t,J＝7.6Hz,2H)、6.78(t,J＝7.6Hz,1H)、4.52-4.43(m,2H)、3.99(s,3H)、1.39(t,J＝7.2Hz,3H)

Production example 7 Synthesis of EMIm _ PI

0.8g (3.2mmol) of 1-ethyl-3-methylimidazolium lactate (manufactured by Tokyo chemical industry Co., Ltd.), l.l.g (9.5mmol) of phenylisocyanate and 3.3g of chlorobenzene were charged, and the mixture was stirred at 20 ℃ for 20 minutes. After stirring, the resulting reaction mixture was concentrated under reduced pressure to obtain 1.9g of a brown liquid. The resulting brown liquid was separated by an alumina column to obtain EMIm _ PI.

[ reference preparation example 1] Synthesis of 1-methyl-3-octylimidazolium-2-N-phenylamide salt (OMIm _ PI)

[ solution 67]

A500 mL autoclave purged with nitrogen was charged with 93.1g (0.5mol) of 1-octylimidazole, 93.0g (1.0mol) of dimethyl carbonate and 93. g of methanol, and stirred at 135 ℃ for 24 hours. After the obtained reaction mixture was cooled to a boiling point of the solvent or less, it was concentrated under reduced pressure and the obtained solid was washed 3 times with 150mL of hexane and dried, whereby 133.2g of 1-methyl-3-octylimidazolium-2-carboxylate was obtained. Subsequently, 50.0g (210mmol) of the 1-methyl-3-octylimidazolium-2-carboxylate and 500mL of toluene were charged into a 200mL three-necked flask purged with nitrogen, heated to 110 ℃ and then stirred for 1 hour after 25.1g (211mmol) of phenylisocyanate was added dropwise over 2 hours. After the resulting reaction mixture was cooled to 25 ℃, concentrated under reduced pressure and recrystallized by adding 150.5g of butyl acetate, 26.5g of the compound represented by the above formula (OMIm _ PI) was obtained. Of a compound represented by the above formula¹The results of H-NMR analysis are shown below.

¹H-NMR(CD₃OD)δ(ppm)＝7.51(s,1H)、7.45―7.33(m,6H)、4.37(t,J＝7.4Hz,2H)、3.97(s,3H)、1.91-1.86(m,2H)、1.35-1.27(m,10H)、0.88(t,J＝6.8Hz,3H)

[ example 1]

A thermosetting composition was prepared by mixing 1.85g of polyester polyol (available from Toyo Boseki Co., Ltd., VYLON GK-68HA, hydroxyl value 12.8mgKOH/g), 0.15g of blocked isocyanate (available NCO: 12.4 wt% available from Asahi chemical Co., Ltd., DURANATE TPA-B80E) and 0.04g of DOIm _ PI obtained in preparation example 1 in the composition shown in Table 1. The obtained thermosetting composition was baked, and then compatibility and solvent resistance were evaluated, and the results are shown in table 1.

[ example 2]

A thermosetting composition was prepared in the same manner as in example 1, except that D2EHIm _ PI obtained in production example 2 was used instead of DOIm _ PI in production example 1. The obtained thermosetting composition was baked, and then compatibility and solvent resistance were evaluated, and the results are shown in table 1.

[ example 3]

A thermosetting composition was prepared in the same manner as in example 1, except that the dbnimi _ PI obtained in production example 3 was used instead of the DOIm _ PI in production example 1. The obtained thermosetting composition was baked, and then compatibility and solvent resistance were evaluated, and the results are shown in table 1.

[ example 4]

A thermosetting composition was prepared in the same manner as in example 1, except that the DBIm _ PI obtained in production example 4 was used instead of DOIm _ PI in production example 1. The obtained thermosetting composition was baked, and then compatibility and solvent resistance were evaluated, and the results are shown in table 1.

Comparative example 1 evaluation of thermosetting composition containing known catalyst

A thermosetting composition was obtained in the same manner as in example 1, except that dibutyltin dilaurate (DBTDL) was used instead of DOIm _ PI in production example 1. The obtained thermosetting composition was baked, and then compatibility and solvent resistance were evaluated, and the results are shown in table 1.

[ reference example 1] evaluation of thermosetting composition containing 1-methyl-3-octylimidazolium-2-N-phenylamide salt (OMIm _ PI)

A thermosetting composition was prepared in the same manner as in example 1, except that 1-methyl-3-octylimidazolium-2-N-phenylamide salt (OMIm _ PI) obtained in reference production example 1 was used instead of DOIm _ PI in production example 1. The obtained thermosetting composition was baked, and then compatibility and solvent resistance were evaluated, and the results are shown in table 1.

In table 1, compatibility "a" indicates that the coating film was not clouded, solvent resistance "a" indicates that the aluminum plate as the coating object was not exposed at all, and "C" indicates that the aluminum plate was exposed.

[ Table 1]

As is apparent from comparison of examples 1 to 4 in Table 1 with reference example 2, no mixing of the coating films containing DOIm _ PI, D2EHIm _ PI, DBnIm _ PI and DBIm _ PI is observed, wherein DOIm _ PI, D2EHIm _ PI, DBnIm _ PI and DBIm _ PI are the amide-based compound (4) of the present invention, and R of the nitrogen-containing organic group represented by the formula (2)¹And R⁴The number of carbon atoms of (A) is 2 to 30, particularly 2 to 20. On the other hand, a coating film containing OMIm _ PI, which is an amide compound (4) and R of a nitrogen-containing organic group represented by the formula (2), is turbid¹Has 1 carbon atom. As described above, in the amide-based compound (4) of the present invention, in particular, R of the nitrogen-containing organic group represented by the formula (2) is used in view of improving compatibility with a urethane resin and a mixture of a blocked isocyanate and a compound having an isocyanate-reactive group¹And R⁴The amide-based compound having 2 to 30 carbon atoms is excellent.

Further, as is apparent from a comparison of examples 1 to 4 of Table 1 with reference example 1, R comprising the amide-based compound (4) of the present invention, particularly the nitrogen-containing organic group represented by the formula (2) therein, is contained as compared with a coating film comprising a known catalyst¹And R⁴The amide-based compound having 2 to 30 carbon atoms has excellent solvent resistance and excellent catalytic activity.