Amphoteric compounds and blocking agent dissociation catalysts for blocked isocyanates, blocked isocyanate compositions containing the blocking agent dissociation catalyst, thermosetting resin compositions, cured products and methods for producing the same, and carbonate compounds

Abstract

The present invention provides a blocking agent dissociation catalyst for a blocked isocyanate, the blocking agent dissociation catalyst containing a zwitterionic compound represented by formula (1). Formula (1): (In the formula, A, R1, R2, X, B1, and a are as defined in the specification.)

Description

[Technical Field]

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

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

[0003] As mentioned above, blocked isocyanates require heating to dissociate the blocking agent. However, in recent years, there has been a demand for lower dissociation temperatures of the blocking agent to reduce energy consumption and costs. Therefore, attempts have been made to use catalysts to lower the dissociation temperature of the blocking agent in blocked isocyanates. Metal organic acid salts are known as such blocking agent dissociation catalysts. Among metal organic acid salts, organotin catalysts such as dibutyltin dilaurylate are often used (Non-Patent Literature 1). However, when the inventors used dibutyltin dilaurylate as a blocking agent dissociation catalyst and measured the curing time of a thermosetting resin composition containing a polyol and a blocked isocyanate at 120°C, curing did not occur even after 90 minutes, and its catalytic activity was not satisfactory (see Comparative Example 1). Furthermore, organotin catalysts are highly toxic, and their harmful effects on the environment and human health are a concern. There are already movements, mainly in Europe, to regulate the use of organotin catalysts in the manufacture of polyurethane resins, and there is a demand for catalysts that can replace organotin catalysts. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] "Latest Application Technologies of Liquid Polyurethane," Chunichi-sha Publishing, 1989, pp. 262-265. [Overview of the project] [Problems that the invention aims to solve]

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

[0006] The inventors intensively studied to solve the above problems. As a result, when the zwitterionic compound represented by the formula (1) was used as a blocking dissociation catalyst for blocked isocyanate, it was found that excellent low-temperature dissociation properties were exhibited, and the present invention was completed.

[0007] The present invention provides the following zwitterionic compound, a blocking agent dissociation catalyst for blocked isocyanate, a blocked isocyanate composition containing the blocking agent dissociation catalyst, a thermosetting resin composition, a cured product, and a method for producing the same. 〔1〕 A blocking agent dissociation catalyst for blocked isocyanate containing a zwitterionic compound represented by the following formula (1). Formula (1):

[0008]

Chemical formula

[0009] (In the formula, R 3 , 4 , + , , 4 , 5 , 3 represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. When X is a nitrogen atom, a represents 1, and when X is an oxygen atom, a represents 0. R 2 represents a substituted or unsubstituted divalent hydrocarbon group. B 1 represents a cationic group represented by the formula (2) or the formula (3). n is an integer of 1 or more. A represents an n-valent substituted or unsubstituted hydrocarbon group.) Formula (2):

[0010] ​​​​​​​​​​​​​​​​​​​​​5 Some or all of them may be mutually bonded to form a ring structure.) Formula (3):

[0012] [Chemical formula]

[0013] (In the formula, R 8 represents a bond with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted hydrocarbon group having a bond with R 2 . R 6 , R 7 , and R 9 are the same or different and represent a bond with R 2 , a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted hydrocarbon group having a bond with R 2 . Any one of R[[ID=三十二]] 6 [[ID=三十三]] 7 [[ID=三十五]] 8 [[ID=三十七]] 9 [[ID=三十九]] 2 [[ID=四十一]] 2 [[ID=四十三]] 6 [[ID=四十五]] 7 [[ID=四十七]] 8 [[ID=四十九]] 9 [[ID=五十一]] 6 [[ID=五十三]] 7 [[ID=五十五]] 8 [[ID=五十七]] 9 [[ID=五十九]] 6 [[ID=六十一]] 7 [[ID=六十三]] 8 [[ID=六十五]] 9 [[ID=六十七]]<0000circumstances where some or all of them are mutually bonded to form a ring structure, and among R[[ID=六十八]] 2 [[ID=六十九]] 2 [[ID=七十一]]<0circumstances where some or all of them are mutually bonded to form a ring structure, and among R[[ID=六十八]] 2 [[ID=六十九]] 2 [[ID=七十一]] 2 [[ID=七十三]] + [[ID=七十五]]represents a nitrogen cation or a phosphorus cation.)[[ID=七十六]] [[ID=七十七]][2][[ID=七十八]] [[ID=七十九]]Y[[ID=八十]] + ​​​​​​​​​​​​​​​​​The blocking agent dissociation catalyst for blocked isocyanates according to [1], wherein is a nitrogen cation, or the cationic group represented by formula (3) is a group represented by formula (3-1), formula (3-2), formula (3-1a), or formula (3-2a). Formula (3-1):

[0014] [ka]

[0015] (R 7 is R 2 A bond with, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 8 , R 10 , R 11 and R 12 They are the same or different, R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 7 , R 8 , R 10 , R 11 and R 12 One of the following is R 2 A joint or R that connects to it 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 7 , R 8 , R 10 , R 11 and R 12 If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure. Formula (3-2):

[0016] [ka]

[0017] (R 7 is R 2 A bond with, a substituted or unsubstituted hydrocarbon group, or R 2represents a substituted or unsubstituted hydrocarbon group having a bonding hand with R 8 R 13 R 14 R 15 and R 16 are the same or different and represent a bonding hand with R 2 , a hydrogen atom, a substituted or unsubstituted hydrocarbon group or a substituted or unsubstituted hydrocarbon group having a bonding hand with R 2 R 7 R 8 R 13 R 14 R 15 and R 16 any one of which is a bonding hand bonding with R 2 or a substituted or unsubstituted hydrocarbon group having a bonding hand with R 2 R 7 R 8 R 13 R 14 R 15 and R 16 When R Formula (3-1a), Formula (3-2a):[[ID=)45]]

[0018] [[ID=)47]] [[ID=)48]] [[ID=)49]]

Chemical formula

[0019] [[ID=)55]] [[ID=)56]](In the formula, R[[ID=)57]] 7 [[ID=)58]]R[[ID=)59]] 8 [[ID=)60]]R[[ID=)61]] 10 [[ID=)62]]R[[ID=)63]] 13 [[ID=)64]]and R[[ID=)65]] 14 [[ID=)66]]are as defined above. R[[ID=)67]] w [[ID=)68]]R[[ID=)69]] x [[ID=)70]]R[[ID=)71]] y [[ID=)72]]and R[[ID=)73]] z [[ID=)74]]each represent a bonding hand with R[[ID=)75]] 2 [[ID=)76]], a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)[[ID=)77]] [[ID=)78]]〔3〕[[ID=)79]] A is a blocking agent dissociation catalyst for blocked isocyanates according to [1] or [2], wherein A is an n-valent substituted or unsubstituted aliphatic hydrocarbon group, an n-valent substituted or unsubstituted alicyclic hydrocarbon group, an n-valent substituted or unsubstituted aromatic hydrocarbon group, or an n-valent substituted or unsubstituted aromatic aliphatic hydrocarbon group. [4] A blocking agent dissociation catalyst for blocked isocyanates according to any one of items [1] to [3], wherein n is 1 to 20. [5] A blocking agent dissociation catalyst for blocked isocyanates according to any one of items [1] to [4], wherein X is a nitrogen atom. [6] A blocked isocyanate composition containing a blocking agent dissociation catalyst and a blocked isocyanate compound as described in any one of items [1] to [5]. [7] The blocked isocyanate composition according to [6], wherein the blocked isocyanate compound is blocked with at least one blocking agent selected from the group consisting of alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds. [8] The blocked isocyanate composition according to [6] or [7], wherein the blocked isocyanate compound is a blocked isocyanate compound blocked with a fluoride alcohol compound. [9] A thermosetting resin composition comprising a blocked isocyanate composition according to any one of items [6] to [8] and a compound having an isocyanate-reactive group.

[10] The thermosetting resin composition according to [9], wherein the compound having an isocyanate reactive group is a polyol compound.

[11] A cured product obtained by curing the thermosetting resin composition described in [9] or

[10] .

[12] A method for producing a cured product, comprising a step of heating and curing the thermosetting resin composition according to [9] or

[10] .

[13] An amphoteric ion compound represented by the following formula (1). Formula (1):

[0020] [Chemical formula]

[0021] (In the formula, R 1 represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. When X is a nitrogen atom, a represents 1, and when X is an oxygen atom, a represents 0. R 2 represents a substituted or unsubstituted divalent hydrocarbon group. B 1 represents a cationic group represented by formula (2) or formula (3). n is an integer of 1 or more. A represents an n-valent substituted or unsubstituted hydrocarbon group.) Formula (2):

[0022] [Chemical formula]

[0023] (In the formula, Y + represents a nitrogen cation or a phosphorus cation. R 3 , R 4 and R 5 are the same or different and represent a substituted or unsubstituted hydrocarbon group. Also, R 3 , R 4 and R 5 may be partially or entirely bonded to each other to form a ring structure.) Formula (3):

[0024] <​​​​​​​​​​​​A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 A substituted or unsubstituted hydrocarbon group having a bond with R 6 , R 7 and R 9 They are the same or different, R 2 A bond with, a substituted or unsubstituted hydrocarbon group or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 6 , R 7 , R 8 , and R 9 One of the following is R 2 A joint or R 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 6 , R 7 , R 8 and R 9 Some or all of these may be bonded to each other to form a ring structure. 6 , R 7 , R 8 and R 9 When some or all of the elements are bonded to each other to form a ring structure, 6 , R 7 , R 8 and R 9 Of these, the groups that do not form the ring structure are R 2 A joint or R 2 If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R 2 It has a bonding hand that connects to Z. + (This indicates a nitrogen cation or a phosphorus cation.)

[14] Y + The amphoteric compound according to

[13] , wherein is a nitrogen cation, or the cationic group represented by formula (3) is a group represented by formula (3-1), formula (3-2), formula (3-1a), or formula (3-2a). Formula (3-1):

[0026] [ka]

[0027] (R 7 is R 2 A bond with, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 8 , R 10 , R 11 and R 12 They are the same or different, R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 7 , R 8 , R 10 , R 11 and R 12 One of the following is R 2 A joint or R that connects to it 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 7 , R 8 , R 10 , R 11 and R 12 If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure. Formula (3-2):

[0028] [ka]

[0029] (R 7 is R 2 A bond with, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 8 , R 13 , R 14 , R 15 and R 16 They are the same or different, R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 7 , R 8 , R 13 , R14 , R 15 and R 16 One of the following is R 2 A joint or R that connects to it 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 7 , R 8 , R 13 , R 14 , R 15 and R 16 If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure. Equation (3-1a), Equation (3-2a):

[0030] [ka]

[0031] (In the formula, R 7 , R 8 , R 10 , R 13 and R 14 This is as defined above. R w , R x , R y and R z These are R 2 (This indicates a bond with a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[15] The amphoteric compound according to

[13] or

[14] , wherein A is an n-valent substituted or unsubstituted aliphatic hydrocarbon group, an n-valent substituted or unsubstituted alicyclic hydrocarbon group, an n-valent substituted or unsubstituted aromatic hydrocarbon group, or an n-valent substituted or unsubstituted aromatic aliphatic hydrocarbon group.

[16] An amphoteric compound as described in any one of items

[13] to

[15] , wherein n is 1 to 20.

[17] An amphoteric compound as described in any one of the items

[13] to

[16] , wherein X is a nitrogen atom.

[18] R 2However, the amphoteric compound described in any one of items

[13] to

[17] is a substituted or unsubstituted divalent alkylene group.

[19] A method for producing an amphoteric compound represented by formula (1), comprising stirring the compound represented by formula (8) in a solvent.

[0032] [ka]

[0033] (In the formula, R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.)

[0034] R 1 represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. If X is a nitrogen atom, a represents 1; if X is an oxygen atom, a represents 0. 2 represents a substituted or unsubstituted divalent hydrocarbon group. 1 represents a cationic group represented by formula (2) or formula (3). n is an integer of 1 or more. A represents an n-valent substituted or unsubstituted hydrocarbon group. Formula (2):

[0035] [ka]

[0036] (In the formula, Y + R represents a nitrogen cation or a phosphorus cation. 3 , R 4 and R 5 These represent identical or different substituted or unsubstituted hydrocarbon groups. Also, R 3 , R 4 and R 5 (Some or all of these may be bonded to each other to form a ring structure.) Formula (3):

[0037] [ka]

[0038] (In the formula, R 8 R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 R represents a substituted or unsubstituted hydrocarbon group having a bond with the following: 6 , R 7 , and R 9 They are the same or different, R 2 A bond with, a substituted or unsubstituted hydrocarbon group or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 6 , R 7 , R 8 , and R 9 One of the following is R 2 A joint or R 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 6 , R 7 , R 8 and R 9 Some or all of these may be bonded to each other to form a ring structure. 6 , R 7 , R 8 and R 9 When some or all of the elements are bonded to each other to form a ring structure, 6 , R 7 , R 8 and R 9 Of these, the groups that do not form the ring structure are R 2 A joint or R 2 If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R 2 It has a bonding hand that connects to Z. + (This indicates a nitrogen cation or a phosphorus cation.)

[20] The method according to

[19] , further comprising the step of reacting a compound represented by formula (6) with a carbonate ester compound represented by formula (7a) or formula (7b) to produce a compound represented by formula (8).

[0039] [ka]

[0040] (In the formula, B 1x B is a group represented by the following formula (10) or formula (11). 1x The following formula In the case of the group represented by (10), use the carbonate ester compound represented by formula (7a), B 1x If the group is represented by formula (11) below, use the carbonate ester compound represented by formula (7b). R' is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, R 3 or R 7 This indicates R 3 R indicates a substituted or unsubstituted hydrocarbon group. 7 This indicates a substituted or unsubstituted hydrocarbon group. R 1 , R 2 , R ‘ B 1 (A, a, X, and n are as defined above.) Equation (10):

[0041] [ka]

[0042] (In the formula, Y represents a nitrogen atom or a phosphorus atom. R 4 and R 5 (As defined above.) Equation (11):

[0043] [ka]

[0044] (In the formula, Z represents a nitrogen atom or a phosphorus atom. R 6 , R 8 and R 9 (As defined above.) 〔twenty one〕 The method according to

[19] , further comprising the step of reacting a compound represented by formula (9) with an isocyanate compound represented by formula (5) to obtain a compound represented by formula (8). Formula (9):

[0045] [ka]

[0046] (In the formula, A, R', a, n, X, B 1 , R 1 , and R 2 (As defined above.) 〔twenty two〕 The compound represented by the following formula (8).

[0047] [ka]

[0048] (In the formula, R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. 1 represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. If X is a nitrogen atom, a represents 1; if X is an oxygen atom, a represents 0. 2 represents a substituted or unsubstituted divalent hydrocarbon group. 1 represents a cationic group represented by formula (2) or formula (3). n is an integer of 1 or more. A represents an n-valent substituted or unsubstituted hydrocarbon group. Formula (2):

[0049] [ka]

[0050] (In the formula, Y + R represents a nitrogen cation or a phosphorus cation. 3 , R 4 and R 5These represent identical or different substituted or unsubstituted hydrocarbon groups. Also, R 3 , R 4 and R 5 (Some or all of these may be bonded to each other to form a ring structure.) Formula (3):

[0051] [ka]

[0052] (In the formula, R 8 R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 A substituted or unsubstituted hydrocarbon group having a bond with R 6 , R 7 and R 9 They are the same or different, R 2 A bond with, a substituted or unsubstituted hydrocarbon group or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 6 , R 7 , R 8 , and R 9 One of the following is R 2 A joint or R 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 6 , R 7 , R 8 and R 9 Some or all of these may be bonded to each other to form a ring structure. 6 , R 7 , R 8 and R 9 When some or all of the elements are bonded to each other to form a ring structure, 6 , R 7 , R 8 and R 9 Of these, the groups that do not form the ring structure are R 2 A joint or R 2 If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R 2 It has a bonding hand that connects to Z. +(This indicates a nitrogen cation or a phosphorus cation.) [Effects of the Invention]

[0053] This invention provides a catalyst that exhibits excellent low-temperature dissociation properties of the blocking agent of blocked isocyanates. Furthermore, it provides a blocked isocyanate composition containing the blocking agent dissociation catalyst, a thermosetting resin composition containing the blocked isocyanate composition that exhibits excellent low-temperature curing properties, a cured product, and a method for producing the same. [Brief explanation of the drawing]

[0054] [Figure 1] The 1H-NMR analysis results for manufacturing example A-3 of this application are shown. [Figure 2] The results of the IR analysis for manufacturing example A-3 of this application are shown. [Figure 3] The 1H-NMR analysis results for manufacturing example A-4 of this application are shown. [Figure 4] The results of the IR analysis for manufacturing example A-4 of this application are shown. [Modes for carrying out the invention]

[0055] <Blocking agent dissociation catalyst for blocked isocyanates> As the blocking agent dissociation catalyst for blocked isocyanates of the present invention, an amphoteric compound represented by formula (1) (hereinafter referred to as amphoteric compound (1)) can be used. Formula (1):

[0056] [ka]

[0057] (In the formula, R 1 represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. If X is a nitrogen atom, a represents 1; if X is an oxygen atom, a represents 0. 2 represents a substituted or unsubstituted divalent hydrocarbon group. 1represents a cationic group represented by formula (2) or formula (3). n is an integer of 1 or more. A represents an n-valent substituted or unsubstituted hydrocarbon group. Formula (2):

[0058] [ka]

[0059] (In the formula, Y + R represents a nitrogen cation or a phosphorus cation. 3 , R 4 and R 5 These represent identical or different substituted or unsubstituted hydrocarbon groups. Also, R 3 , R 4 and R 5 (Some or all of these may be bonded to each other to form a ring structure.) Formula (3):

[0060] [ka]

[0061] (In the formula, R 8 R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 A substituted or unsubstituted hydrocarbon group having a bond with R 6 , R 7 and R 9 They are the same or different, R 2 A bond with, a substituted or unsubstituted hydrocarbon group or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 6 , R 7 , R 8 , and R 9 One of the following is R 2 A joint or R 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 6 , R 7 , R 8 and R 9Some or all of these may be bonded to each other to form a ring structure. 6 , R 7 , R 8 and R 9 When some or all of the elements are bonded to each other to form a ring structure, 6 , R 7 , R 8 and R 9 Of these, the groups that do not form the ring structure are R 2 A joint or R 2 If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R 2 It has a bonding hand that connects to Z. + (This indicates a nitrogen cation or a phosphorus cation.) One example is in equations (1), (2), and (3), where R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 When is a substituted or unsubstituted hydrocarbon group, it 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.

[0062] Another example is in equations (1), (2), (3), (3-1), and (3-2), where R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9The group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0063] Examples of "unsubstituted hydrocarbon groups" include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, decyl group, dodecyl group, octadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, tolyl group, and allyl group.

[0064] Examples of "unsubstituted aliphatic hydrocarbon groups" include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, dodecyl, octadecyl, and allyl groups.

[0065] Examples of "unsubstituted alicyclic hydrocarbon groups" include cyclopropyl groups, cyclopentyl groups, and cyclohexyl groups.

[0066] Examples of "unsubstituted aromatic hydrocarbon groups" include phenyl groups, naphthyl groups, and tolyl groups.

[0067] Examples of "unsubstituted aromatic aliphatic hydrocarbon groups" include the benzyl group and the phenethyl group.

[0068] In this specification, examples of "substituents" include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; alkylamino groups such as methylamino groups; dialkylamino groups such as dimethylamino groups; alkoxy groups such as methoxy and ethoxy groups; aryloxy groups such as phenoxy and naphthyloxy groups; aralkyloxy groups such as benzyloxy and naphthylmethoxy groups; halogenated alkyl groups such as trifluoromethyl groups; nitro groups; cyano groups; sulfonyl groups; alkylcarbonylamino groups; alkyloxycarbonylamino groups; (alkylamino)carbonylamino groups; or (dialkylamino)carbonylamino groups.

[0069] Also, R 1 ~R 16 The monovalent or divalent hydrocarbon group may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. 1 ~R 16 When the hydrocarbon group is substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has at least one of the following groups: -O-, -N<, -NH-, -S-, -SO2-, etc., and the hydrocarbon chain is interrupted by these groups.

[0070] Examples of the alkyl portion of the alkylamino group, dialkylamino group, alkoxy group, halogenated alkyl group, alkylcarbonylamino group, alkyloxycarbonylamino group, (alkylamino)carbonylamino group, and (dialkylamino)carbonylamino group include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, heptyl, octyl, and 2-ethylhexyl. The number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 or 2.

[0071] Examples of the aryl portion of the above-mentioned aryloxy group include aryl groups having 6 to 10 carbon atoms. Specifically, examples of aryl portions include phenyl groups and naphthyl groups.

[0072] Examples of the aralkyl portion of the above-mentioned aralkyloxy group include aralkyl groups having 7 to 12 carbon atoms. Specifically, examples of aralkyl groups include benzyl groups and naphthylmethyl groups.

[0073] In formula (1), R 2 is a substituted or unsubstituted divalent hydrocarbon group, preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms.

[0074] Another mode is, R 2 The group is a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0075] In yet another form, in equation (1), R 2 is a hydrogen atom, or a substituted or unsubstituted divalent alkylene group, preferably a substituted or unsubstituted divalent alkylene group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted divalent alkylene group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted divalent alkylene group having 1 to 30 carbon atoms.

[0076] In formula (1), B 1 represents a cationic group represented by formula (2) or formula (3).

[0077] In formula (2), Y +This is a nitrogen cation or a phosphorus cation, preferably a nitrogen cation.

[0078] In formula (2), R 3 , R 4 and R 5 is a substituted or unsubstituted hydrocarbon group. Preferably, the substituted or unsubstituted hydrocarbon group is 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.

[0079] Another mode is in equation (2), R 3 , R 4 and R 5 The substituted or unsubstituted hydrocarbon group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0080] Examples of cationic groups represented by formula (2) include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, tripentylammonium, trihexylammonium, triheptylammonium, trioctylammonium, trinonylammonium, tri(decyl)ammonium, N-ethyl-N,N-dimethylammonium, N,N-dimethyl-N-propylammonium, N-butyl-N,N-dimethylammonium, N,N-diethyl-N-decylammonium, N,N-diethyl-N-eicosylammonium, N,N-dibutyl-N-pentylammonium, N,N-dibutyl-N-hexylammonium, N,N-dibutyl-N-heptylammonium, N,N-dibutyl-N-octylammonium, N,N-dibutyl-N-nonylammonium, and N,N-dibutyl-N-decylammonium. Examples of these groups include N,N-dibutyl-N-eicosylammonium group, N-ethyl-N-methyl-N-propylammonium group, N-butyl-N-ethyl-N-methylammonium group, trimethylphosphonium group, triethylphosphonium group, tripropylphosphonium group, tributylphosphonium group, tripentylphosphonium group, trihexylphosphonium group, triheptylphosphonium group, trioctylphosphonium group, trinonylphosphonium group, tri(decyl)phosphonium group, tributyloctylphosphonium group, di-n-butyl-n-hexylphosphonium group, dibutyldodecylphosphonium group, dihexyltetradecylphosphonium group, etc. Preferably, the group is trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, tripentylammonium, or trihexylammonium, and particularly preferably, the group is trimethylammonium.

[0081] In formula (3), Z + This is a nitrogen cation or a phosphorus cation, preferably a nitrogen cation.

[0082] In formula (3), R 8 R 2A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 It is a substituted or unsubstituted hydrocarbon group having a bond with R. 6 , R 7 and R 9 They are the same or different, R 2 A bond with, a substituted or unsubstituted hydrocarbon group or R 2 It is a substituted or unsubstituted hydrocarbon group having a bond with . Preferably, the substituted or unsubstituted hydrocarbon group is 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.

[0083] Another example is in equation (3), R 6 , R 7 , R 8 and R 9 When is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0084] Another aspect is that in equation (3), R 6 , R 7 , R 8 and R 9 R 2 In the case of a substituted or unsubstituted hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms having a bond with R, more preferably substituted or R 2An unsubstituted hydrocarbon group having 1 to 50 carbon atoms having a bond with R 2 It is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms that has a bond with the following:

[0085] Another aspect is that in equation (3), R 6 , R 7 , R 8 and R 9 is R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms and having a bond with R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms and having a bond with R, and particularly preferably R 2 It is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms and having a bond with the other.

[0086] In equation (3), R 6 , R 7 , R 8 and R 9 Some or all of them may be bonded to each other to form a ring structure. For example, R 6 and R 9 When these elements bond to each other to form a ring structure, they can take on structures such as those shown in formulas (3a), (3b), or (3c) below. Equation (3a), Equation (3b), Equation (3c):

[0087] [ka]

[0088] (In the formula, R 7 , R 8 As defined above, R a is R2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 This indicates a substituted or unsubstituted hydrocarbon group having a bond with E. 1 , E 2 , E 3 is a substituted or unsubstituted divalent hydrocarbon group or R 2 A substituted or unsubstituted divalent hydrocarbon group having a bond with (G represents an oxygen atom or a sulfur atom). E 1 , E 2 , E 3 is a divalent hydrocarbon group containing substituents or R 2 If the divalent hydrocarbon group has a bond with and contains a substituent, it is preferable that the substituent is bonded to a carbon atom constituting the ring. 1 , E 2 , E 3 The number of substituents attached to it is one, two, or three.

[0089] E 1 , E 2 , E 3 In this case, a divalent hydrocarbon group, R 2 In the case of a divalent hydrocarbon group having a bond with a divalent hydrocarbon group, the divalent hydrocarbon group may be substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. 1 , E 2 , E 3 When the hydrocarbon group is substituted with at least one heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has at least one of the following groups: -O-, -N<, -NH-, -S-, etc., and the divalent hydrocarbon chain is interrupted by these groups.

[0090] R a In this context, the substituted or unsubstituted hydrocarbon groups are preferably substituted or unsubstituted hydrocarbon groups having 1 to 100 carbon atoms, more preferably substituted or unsubstituted hydrocarbon groups having 1 to 50 carbon atoms, and particularly preferably substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms.

[0091] Another example is Ra When is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0092] Another mode is R a R 2 In the case of a substituted or unsubstituted hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms having a bond with R, more preferably substituted or R 2 An unsubstituted hydrocarbon group having 1 to 50 carbon atoms having a bond with R 2 It is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms that has a bond with the following:

[0093] Another mode is R a R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms and having a bond with R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms and having a bond with R, and particularly preferably R 2 It is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms and having a bond with the other.

[0094] E 1 , E 2 , E 3 In this context, the substituted or unsubstituted divalent hydrocarbon group is preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms.

[0095] Another example is E 1 , E 2 , E 3 When is a substituted or unsubstituted divalent hydrocarbon group, the substituted or unsubstituted divalent hydrocarbon group is a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 6 carbon atoms.

[0096] Another mode is E 1 , E 2 , E 3 R 2 In the case of a substituted or unsubstituted hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms having a bond with R, more preferably substituted or R 2 An unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms having a bond with R, and particularly preferably R 2 It is a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms that has a bond with .

[0097] Another mode is E 1 , E2 , E 3 R 2 A substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 20 carbon atoms and having a bond with R 2 A substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 12 carbon atoms and having a bond with R, and particularly preferably R 2 It is a substituted or unsubstituted divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 6 carbon atoms and having a bond with .

[0098] The above is R 6 and R 9 This is an example of a case where R is bonded to each other to form a ring structure. 6 and R 7 , R 7 and R 8 , R 8 and R 9 Similarly, a ring structure can be formed when the elements bond to each other to form a ring structure.

[0099] The cationic group represented by formula (3) is preferably a cationic group represented by the following formula (3-1) or formula (3-2), and particularly preferably a cationic group represented by the following formula (3-1). Formula (3-1):

[0100] [ka]

[0101] (R 7 is R 2 R indicates a bond with, or a substituted or unsubstituted hydrocarbon group. 8 , R 10 , R 11 and R 12They are the same or different, R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 7 , R 8 , R 10 , R 11 and R 12 One of the following is R 2 A joint or R that connects to it 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 7 , R 8 , R 10 , R 11 and R 12 If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure. Formula (3-2):

[0102] [ka]

[0103] (R 7 is R 2 R indicates a bond with, or a substituted or unsubstituted hydrocarbon group. 8 , R 13 , R 14 , R 15 and R 16 They are the same or different, R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 R indicates a substituted or unsubstituted hydrocarbon group having a bond with the following: 7 , R 8 , R 13 , R 14 , R 15 and R 16 One of the following is R 2 A joint or R that connects to it 2 It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. 7 , R 8 , R 13 , R 14 , R 15 and R16 If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure.

[0104] In formula (3-1), R 7 R 2 It is a bond with, or a substituted or unsubstituted hydrocarbon group. 8 , R 10 , R 11 and R 12 They are the same or different, R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2 It is a substituted or unsubstituted hydrocarbon group having a bond with . Preferably, the substituted or unsubstituted hydrocarbon group is 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.

[0105] Another example is in equation (3-1), R 7 , R 8 , R 10 , R 11 and R 12 When is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0106] Another aspect is that in equation (3-1), R 7 , R 8 , R 10 , R 11 and R 12 R2 In the case of a substituted or unsubstituted hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms having a bond with R, more preferably substituted or R 2 An unsubstituted hydrocarbon group having 1 to 50 carbon atoms having a bond with R 2 It is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms that has a bond with the following:

[0107] Another aspect is that in equation (3-1), R 7 , R 8 , R 10 , R 11 and R 12 R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms and having a bond with R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms and having a bond with R, and particularly preferably R 2 It is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms and having a bond with the other.

[0108] The cationic groups represented by formula (3-1) include, specifically, 1,3-dimethylimidazolium group, 1-ethyl-3-methylimidazolium group, 1-methyl-3-propylimidazolium group, 1-butyl-3-methylimidazolium group, 1-methyl-3-pentylimidazolium group, 1-hexyl-3-methylimidazolium group, 1-heptyl-3-methylimidazolium group, 1-methyl-3-octylimidazolium group, 1-methyl-3-nonylimidazolium group, 1-decyl-3-methylimidazolium group, 1-allyl-3-methylimidazolium group, 1-allyl-3-ethylimidazolium group, and 1-(2-methoxyethyl)-3-methylimidazolium group. Examples include 1-(2-ethoxyethyl)-3-methylimidazolium group, 1-ethyl-3-(2-methoxyethyl)imidazolium group, 1-ethyl-3-(2-ethoxyethyl)imidazolium group, 1,3-di(tert-butyl)imidazolium, 1,3-bis(1,1-dimethylethyl)imidazolium group, 1,3-bis(1,1-dimethylpropyl)imidazolium group, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium group, 1,3-bis(1-methyl-1-phenylethyl)imidazolium group, 1,3-bis(1,1-dimethyl-2-phenylethyl)imidazolium group, and 1,3-bis(1-adamantyl)imidazolium group.

[0109] In formula (3-2), R 7 R 2 A bond with, a substituted or unsubstituted hydrocarbon group or R 2 It is a substituted or unsubstituted hydrocarbon group having a bond with R. 8 , R 13 , R 14 , R 15 and R 16 They are the same or different, R 2 A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R 2It is a substituted or unsubstituted hydrocarbon group having a bond with . Preferably, the substituted or unsubstituted hydrocarbon group is 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.

[0110] Another example is in equation (3-2), R 7 , R 8 , R 13 , R 14 , R 15 and R 16 When is a substituted or unsubstituted hydrocarbon group, the substituted or unsubstituted hydrocarbon group is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms.

[0111] Another aspect is that in equation (3-2), R 7 , R 8 , R 13 , R 14 , R 15 and R 16 R 2 In the case of a substituted or unsubstituted hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms having a bond with R, more preferably substituted or R 2 An unsubstituted hydrocarbon group having 1 to 50 carbon atoms having a bond with R 2 It is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms that has a bond with the following:

[0112] Another aspect is that in equation (3-2), R 7 , R 8 , R 13 , R 14 , R 15 and R 16 is R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having a bond with R, preferably R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 100 carbon atoms and having a bond with R 2 A substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 50 carbon atoms and having a bond with R, and particularly preferably R 2 It is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group having 1 to 30 carbon atoms and having a bond with the other.

[0113] Examples of cationic groups represented by formula (3-2) include 1-methylpyridinium group, 1-ethylpyridinium group, 1-propylpyridinium group, 1-butylpyridinium group, 1-pentylpyridinium group, 1-hexylpyridinium group, 1-heptylpyridinium group, 1-octylpyridinium group, 1-nonylpyridinium group, 1-decylpyridinium group, 1-hexadecylpyridinium group, 1-allylpyridinium group, 1-(2-methoxyethyl)pyridinium group, and 1-(2-ethoxyethyl)pyridinium group.

[0114] R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16These may form a ring structure together with the carbon, nitrogen, or phosphorus atoms to which they are bonded.

[0115] For example, R 11 and R 12 , R 15 and R 16 However, when they combine with the carbon atoms to which they are bonded to form a ring structure, they can take the form of a benzimidazolium ring structure or a quinolinium ring structure, for example, as shown in formula (3-1a) or formula (3-2a) below.

[0116] [ka]

[0117] (In the formula, R 7 , R 8 , R 10 , R 13 and R 14 This is as defined above. R w , R x , R y and R z These are R 2 (This indicates a bond with a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

[0118] The above is R 11 and R 12 , R 15 and R 16 An example of a case where R forms a ring structure is shown below. 1 and R 3 , R 1 and R 7 , R 1 and R 8 , R 3 and R 4 , R 7 and R 8 , R 8 and R 9 , R 8 and R 10 , R 10 and R 11 , R 12 and R 7 , R 13 and R14 Similarly, a ring structure can be formed in this case as well.

[0119] In formula (1), A is a substituted or unsubstituted n-valent hydrocarbon group, preferably a substituted or unsubstituted n-valent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, a substituted or unsubstituted n-valent aromatic hydrocarbon group having 6 to 200 carbon atoms, or a substituted or unsubstituted n-valent aromatic aliphatic hydrocarbon group having 7 to 200 carbon atoms.

[0120] Furthermore, "n-valent hydrocarbon group" refers to the remaining group after n hydrogens have been removed from a hydrocarbon group; "n-valent aliphatic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an aliphatic hydrocarbon group; "n-valent alicyclic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an alicyclic hydrocarbon group; "n-valent aromatic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an aromatic hydrocarbon group; and "n-valent aromatic aliphatic hydrocarbon group" refers to the remaining group after n hydrogens have been removed from an aromatic aliphatic hydrocarbon group.

[0121] In this specification, "substituted or unsubstituted hydrocarbon group" includes (i) a hydrocarbon group which may have substituents, (ii) a hydrocarbon group which may be substituted with a heteroatom, and (iii) a hydrocarbon group which has substituents and is substituted with a heteroatom.

[0122] Furthermore, "substituted or unsubstituted aliphatic hydrocarbon groups" includes (iv) aliphatic hydrocarbon groups which may have substituents, (v) aliphatic hydrocarbon groups which may be substituted with heteroatoms, and (vi) aliphatic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0123] Furthermore, "substituted or unsubstituted alicyclic hydrocarbon groups" includes (vii) alicyclic hydrocarbon groups which may have substituents, (viii) alicyclic hydrocarbon groups which may be substituted with heteroatoms, and (ix) alicyclic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0124] Furthermore, "substituted or unsubstituted aromatic hydrocarbon groups" include (x) aromatic hydrocarbon groups which may have substituents, (xi) aromatic hydrocarbon groups which may be substituted with heteroatoms, and (xii) aromatic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0125] Furthermore, "substituted or unsubstituted aromatic aliphatic hydrocarbon groups" includes (xiii) aromatic aliphatic hydrocarbon groups which may have substituents, (xiv) aromatic aliphatic hydrocarbon groups which may be substituted with heteroatoms, and (xv) aromatic aliphatic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0126] In this specification, "substituted or unsubstituted n-valent hydrocarbon group" includes (i) an n-valent hydrocarbon group which may have substituents, (ii) an n-valent hydrocarbon group which may be substituted with a heteroatom, and (iii) an n-valent hydrocarbon group which has substituents and is substituted with a heteroatom. Furthermore, "substituted or unsubstituted n-valent aliphatic hydrocarbon group" includes (iv) an n-valent aliphatic hydrocarbon group which may have substituents, (v) an n-valent aliphatic hydrocarbon group which may be substituted with a heteroatom, and (vi) an n-valent aliphatic hydrocarbon group which has substituents and is substituted with a heteroatom.

[0127] Furthermore, "substituted or unsubstituted n-valent alicyclic hydrocarbon groups" include (vii) n-valent alicyclic hydrocarbon groups which may have substituents, (viii) n-valent alicyclic hydrocarbon groups which may be substituted with heteroatoms, and (ix) n-valent alicyclic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0128] Furthermore, "substituted or unsubstituted n-valent aromatic hydrocarbon groups" includes (x) n-valent aromatic hydrocarbon groups which may have substituents, (xi) n-valent aromatic hydrocarbon groups which may be substituted with heteroatoms, and (xii) n-valent aromatic hydrocarbon groups which have substituents and are substituted with heteroatoms.

[0129] Furthermore, "substituted or unsubstituted n-valent aromatic aliphatic hydrocarbon group" includes (xiii) an n-valent aromatic aliphatic hydrocarbon group which may have substituents, (xiv) an n-valent aromatic aliphatic hydrocarbon group which may be substituted with a heteroatom, and (xv) an n-valent aromatic aliphatic hydrocarbon group which has substituents and is substituted with a heteroatom.

[0130] In A, unsubstituted n-valent hydrocarbon groups include methane, ethane, propane, isopropane, butane, sec-butane, tert-butane, pentane, hexane, heptane, decane, dodecane, octadecane, cyclopropane, cyclopentane, cyclohexane, benzene, naphthalene, toluene, phenylethane, and propylene, from which n hydrogen atoms have been removed. In the case of toluene and phenylethane, one or both of the hydrogen atoms of the aromatic ring and / or the methyl or ethyl group may be removed. However, if n is 2 or more, the removed hydrogen atoms are hydrogen atoms bonded to different carbon atoms.

[0131] In another form, in formulas (1), (5), (6), and (8), A is a hydrocarbon group excluding the isocyanate group of the following isocyanate compounds (i) to (v). In this specification, isocyanate includes monofunctional isocyanates and polyfunctional isocyanates. (i) Aliphatic isocyanates, (ii) Alicyclic isocyanates, (iii) Aromatic isocyanates, (iv) Aromatic aliphatic isocyanates, (v) A modified isocyanate formed from at least one selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, and aromatic aliphatic isocyanates.

[0132] In this specification, specific examples of preferred groups represented by A are given below.

[0133] [ka]

[0134] In formula (1), formula (2), and formula (3), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 In A, the number of substituents on the hydrocarbon group, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and aromatic aliphatic hydrocarbon group can be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0135] In formula (1), X represents a nitrogen atom or an oxygen atom, preferably a nitrogen atom.

[0136] In formula (1), n ​​is an integer of 1 or more, preferably an integer between 1 and 20, more preferably between 1 and 6, even more preferably between 1 and 4, and particularly preferably 1 or 2.

[0137] Specific examples of the zwitterionic compound (1) are shown below. However, the present invention is not limited to these. In the following specific examples, Et is an ethyl group, Pr is a propyl group, i Pr represents an isopropyl group, Bu represents a butyl group, and Bnz represents a benzyl group.

[0138] [ka]

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[0175] [ka]

[0176] Preferably, the amphoteric compound (1) is (1-2-1a-1)~(1-2-33a-1), (1-2-1b-1)~(1-2-33b-1), (1-2-1c-1)~(1-2-33c-1), (1-2-1a-2)~(1-2-33a-2), (1-2-1b-2)~(1-2-33b-2), (1-2-1c-2)~(1-2-33c-2), (1-2-1a-6)~(1-2-33a The compounds are represented by (1-2-1b-6)~(1-2-33b-6), (1-2-1c-6)~(1-2-33c-6), (1-2-1a-14)~(1-2-33a-14), (1-2-1b-14)~(1-2-33b-14), and (1-2-1c-14)~(1-2-33c-14), with the compounds represented by (1-2-12a-1) and (1-2-12a-2) being particularly preferred.

[0177] One method for producing the zwitterionic compound (1) is to stir the compound represented by formula (8) in a solvent (production method 1).

[0178] [ka]

[0179] (In the formula, R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. 1 , R 2 A, a, X and B 1 (As defined above.) Manufacturing method 1 will be explained.

[0180] The reaction can usually be carried out at temperatures ranging from 0°C to the boiling point of the solvent. The reaction temperature is preferably 20°C to 150°C, more preferably 40°C to 150°C, and even more preferably 40°C to 120°C. In the case of compounds where X = oxygen atom in formula (8), the reaction temperature is preferably 20 to 60°C.

[0181] The reaction time is typically 1 to 20 hours, preferably 1 to 10 hours.

[0182] Examples of solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, acetone, and methanol. The amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (8). Two or more solvents may be mixed and used as needed.

[0183] In the manufacturing method 1 of the present invention, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium, if necessary.

[0184] The resulting zwitterionic compound (1) can be purified by conventional methods such as concentration and recrystallization.

[0185] The compound represented by formula (8) used in manufacturing method 1 may be one that has been prepared by, for example, the following method.

[0186] Method A: A method comprising (Step 1) and (Step 2).

[0187] [ka]

[0188] (In the formula, B 1x B is a group represented by the following formula (10) or formula (11). 1x If the group is represented by formula (10) below, use the carbonate ester compound represented by formula (7a), B 1xIf the group is represented by formula (11) below, use the carbonate ester compound represented by formula (7b). R' is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, R 3 or R 7 This indicates R 1 , R 2 , R 3 , R 7 B 1 (A, a, X, and n are as defined above.)

[0189] (Step 1) A compound represented by formula (4) is reacted with an isocyanate compound represented by formula (5) to obtain a compound represented by formula (6).

[0190] (Step 2) A compound represented by formula (6) is reacted with a carbonate ester compound represented by formula (7a) or formula (7b) to obtain a compound represented by formula (8), wherein in formula (8), R' is R 3 or R 7 A compound (hereinafter referred to as compound (8b')) can be obtained. Compound (8b') is a compound represented by formula (8), and is included in compounds (hereinafter referred to as compound (8b)) in which R' in formula (8) is a substituted or unsubstituted hydrocarbon group. Equation (10):

[0191] [ka]

[0192] (In the formula, Y represents a nitrogen atom or a phosphorus atom. R 4 and R 5 (As defined above.) Equation (11):

[0193] [ka]

[0194] (In the formula, Z represents a nitrogen atom or a phosphorus atom. R 6 , R 8 and R 9(As defined above.)

[0195] (Step 1) will be explained.

[0196] By reacting a compound represented by formula (4) with an isocyanate compound represented by formula (5), a urethane compound or urea compound represented by formula (6) can be obtained.

[0197] Specific examples of compounds represented by formula (4) are shown below. However, the present invention is not limited to these. In the following specific examples, Et is an ethyl group, Pr is a propyl group, i Pr represents an isopropyl group, Bu represents a butyl group, and Bnz represents a benzyl group.

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] X, a, R 1 , R 2 , R 10 It is as defined above. Preferably, X(R 1 ) a is NH or N(CH3), and R 2 is CH2, CH2CH2, CH2(CH2)4, or CH2, and R 10 CH3,Et, i It is Pr, Bu, Bnz, or CH2CH2OCH3.

[0203] [ka]

[0204] X, a, R 1 , R 2 , R 10 As defined above, but preferably X(R 1 ) a is either NH or N(CH3), and R 2 is one of CH2, CH2CH2, or CH2(CH2)4CH2, and R 10 CH3,Et, i It is one of the following: Pr, Bu, Bnz, or CH2CH2OCH3.

[0205] The compound represented by formula (4) is preferably a compound represented by (4-2-1a)~(4-2-33a), (4-2-1b)~(4-2-33b), or (4-2-1c)~(4-2-33c), and is particularly preferably (4-2-12a).

[0206] Specific examples of isocyanate compounds represented by formula (5) are shown below. However, the present invention is not limited to these.

[0207] [ka]

[0208] (In equation (5-9), x is an integer between 0 and 20, preferably between 1 and 20.)

[0209] [ka]

[0210] [ka]

[0211] [ka]

[0212] The isocyanate compound represented by formula (5) is preferably the compound represented by (5-1), (5-2), (5-6), and (5-14), and particularly preferably (5-1), (5-2), and (5-14).

[0213] Specific examples of compounds represented by formula (6) are shown below. However, the present invention is not limited to these. In the following specific examples, Et is an ethyl group, Pr is a propyl group, i Pr represents an isopropyl group, Bu represents a butyl group, and Bnz represents a benzyl group.

[0214] [ka]

[0215] [ka]

[0216] [ka]

[0217] [ka]

[0218] X, a, R 1 , R 2 , R 10 It is as defined above. Preferably, X(R 1 ) a is NH or N(CH3), and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 10 CH3,Et, i It is Pr, Bu, Bnz, or CH2CH2OCH3.

[0219] [ka]

[0220] X, a, R 1 , R 2 , R 10 It is as defined above. Preferably, X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 10 CH3,Et, i It is Pr, Bu, Bnz, or CH2CH2OCH3.

[0221] [ka]

[0222] TIFF0007881582000088.tif20149

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] A, X, a, R 1 , R 2 , R 10 is as defined above. Preferably, A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 10 CH3,Et, i It is Pr, Bu, Bnz, or CH2CH2OCH3.

[0230] [ka]

[0231] A, X, a, R 1 , R 2 , R 10 As defined above. Preferably, A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 10 CH3,Et, i It is Pr, Bu, Bnz, or CH2CH2OCH3.

[0232] [ka]

[0233] TIFF0007881582000097.tif19149

[0234] [ka]

[0235] [ka]

[0236] Preferably, the compound represented by formula (6) is (6-2-1a-1)~(6-2-33a-1), (6-2-1b-1)~(6-2-33b-1), (6-2-1c-1)~(6-2-33c-1), (6-2-1a-2)~(6-2-33a-2), (6-2-1b-2)~(6-2-33b-2), (6-2-1c-2)~(6-2-33c-2), (6-2-1a-6)~(6-2-33a The compounds are represented by (6-2-1b-6)~(6-2-33b-6), (6-2-1c-6)~(6-2-33c-6), (6-2-1a-14)~(6-2-33a-14), (6-2-1b-14)~(6-2-33b-14), and (6-2-1c-14)~(6-2-33c-14), with the compounds represented by (6-2-12a-1) and (6-2-12a-2) being particularly preferred.

[0237] Typically, 0.5 to 10 moles, preferably 0.8 to 3 moles, of the isocyanate compound represented by formula (5) are used for n moles of the compound represented by formula (4).

[0238] The reaction temperature is typically 10 to 200°C or the boiling point of the solvent. Preferably, the reaction temperature is 20 to 150°C.

[0239] The reaction time is typically 1 to 20 hours, preferably 1 to 10 hours.

[0240] A solvent may or may not be used. Examples of solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone. When a solvent is used, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (4).

[0241] In step 1, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium, if necessary.

[0242] The resulting compound represented by formula (6) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for step 2 without purification.

[0243] (Step 2) will be explained.

[0244] In formula (8), R' is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, R 3 or R 7 In the case where R' is a substituted or unsubstituted hydrocarbon group, one mode is that R' 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. Among these, alkyl groups having 1 to 30 carbon atoms are preferred, and alkyl groups having 1 to 6 carbon atoms are more preferred.

[0245] In another configuration, R' is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, preferably a substituted or unsubstituted C1-C100 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, more preferably a substituted or unsubstituted C1-C50 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group, and particularly preferably a substituted or unsubstituted C1-C30 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, or aromatic aliphatic hydrocarbon group. Among these, C1-C30 alkyl groups are preferred, and C1-C6 alkyl groups are more preferred.

[0246] Examples of "unsubstituted hydrocarbon groups" include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, decyl group, dodecyl group, octadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, tolyl group, and allyl group.

[0247] Examples of "unsubstituted aliphatic hydrocarbon groups" include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, dodecyl, octadecyl, and allyl groups.

[0248] Examples of "unsubstituted alicyclic hydrocarbon groups" include cyclopropyl groups, cyclopentyl groups, and cyclohexyl groups.

[0249] Examples of "unsubstituted aromatic hydrocarbon groups" include phenyl groups, naphthyl groups, and tolyl groups.

[0250] Examples of "unsubstituted aromatic aliphatic hydrocarbon groups" include the benzyl group and the phenethyl group.

[0251] Specific examples of carbonate ester compounds represented by formula (7a) or formula (7b) (hereinafter referred to as carbonate ester (7a) or (7b)) include, for example, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, and dihexyl carbonate, and alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate. Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate are preferred, and dimethyl carbonate is particularly preferred.

[0252] Specific examples of compounds represented by formula (8) are shown below. However, the present invention is not limited to these. In the following specific examples, Et is an ethyl group, Pr is a propyl group, i Pr represents an isopropyl group, Bu represents a butyl group, and Bnz represents a benzyl group.

[0253] [ka]

[0254] [ka]

[0255] TIFF0007881582000102.tif6149

[0256] [ka]

[0257] [ka]

[0258] [ka]

[0259] [ka]

[0260] [ka]

[0261] X, a, R 1 , R 2 , R 7 , R 10 R' is as defined above. Preferably, X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, iThe molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0262] [ka]

[0263] X, a, R 1 , R 2、 R 7 , R 10 R' is as defined above. Preferably, X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0264] [ka]

[0265] X, a, R 1 , R 2、 R 7 , R 10 R' is as defined above. Preferably, X(R 1 ) a is NH, N(CH3) or 0, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0266] [ka]

[0267] TIFF0007881582000111.tif20149

[0268]

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[0269]

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[0270]

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[0271]

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[0272]

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[0273]

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[0274]

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[0275]

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[0276]

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[0277]

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[0278] [ka]

[0279] [ka]

[0280] A, X, a, R 1 , R 2 , R 7 , R 10 R' is as defined above. Preferably, A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0281] [ka]

[0282] A, X, a, R 1 , R 2、 R 7 , R 10 R' is as defined above. Preferably, A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0283] [ka]

[0284] A, X, a, R 1 , R 2 , R 10 R' is as defined above. Preferably, A is a group represented by formula (A-2) or a group represented by formula (A-6), and X(R 1 ) a R is either NH, N(CH3), or O, 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0285] [ka]

[0286] TIFF0007881582000127.tif20149

[0287] [ka]

[0288] [ka]

[0289] [ka]

[0290] [ka]

[0291] TIFF0007881582000132.tif52149

[0292] Preferably, as formula (8), (8a-2-1a-1)~(8a-2-33a-1), (8b-2-1a-1)~(8b-2-27a-1), (8a-2-1b-1)~(8a-2-33b-1), (8b-2-1b-1)~(8b-2-27b-1), (8a-2-1c-1)~(8a-2-33c-1), (8b-2-1c-1)~(8b-2-27c-1), (8a-2-1a- 2)~(8a-2-33a-2), (8b-2-1a-2)~(8b-2-27a-2), (8a-2-1b-2)~(8a-2-33b-2), (8b-2-1b-2)~(8b-2-27 b-2), (8a-2-1c-2)~(8a-2-33c-2), (8b-2-1c-2)~(8b-2-27c-2), (8a-2-1a-6)~(8a-2-33a-6), (8b-2-1 a-6)~(8b-2-27a-6), (8a-2-1b-6)~(8a-2-33b-6), (8b-2-1b-6)~(8b-2-27b-6), (8a-2-1c-6)~(8a-2- 33c-6), (8b-2-1c-6)~(8b-2-27c-6), (8a-2-1a-14)~(8a-2-33a-14), (8b-2-1a-14)~(8b-2-27a-14), (8a-2-1b-14)~(8a-2-33b-14), (8b-2-1b-14)~(8b-2-27b-14), (8a-2-1c-14)~(8a-2-33c-14), (8b-2-1c-14)~(8b-2-27c-14), and especially preferably (8a-2-12a-1), (8b-2-10a-1), (8a-2-12a-2), and (8b-2-10a-2).

[0293] The reaction typically uses 0.5 to 10 moles, preferably 0.8 to 3 moles, of the carbonate ester compound represented by formula (7) for every 1 / n mole of the compound represented by formula (6).

[0294] The reaction temperature is typically between 10°C and 120°C, or the boiling point of the solvent.

[0295] The reaction time is typically 1 to 20 hours, preferably 1 to 10 hours.

[0296] Carbonate ester compounds (7a) or (7b) may be used in excess as a solvent, but other solvents may also be used. Examples of solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone. When using other solvents, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (6).

[0297] Step 2 may, if necessary, be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium.

[0298] The obtained compound (8b) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for manufacturing method 1 or step 3 described below without purification.

[0299] After step 2 is completed, the obtained compound (8b) can be used as a raw material for manufacturing method 1, or compound (8b) can be reacted with water to produce a compound in which R' is a hydrogen atom in formula (8) (hereinafter referred to as compound (8a)) (hereinafter referred to as step 3), which can then be used as a raw material for manufacturing method 1.

[0300] In manufacturing method 1, the reaction proceeds more readily with compound (8a) than with compound (8b). Therefore, it is preferable to carry out step 3 to use compound (8a) in manufacturing method 1.

[0301] Let's explain step 3.

[0302] The amount of water used is usually 1 to 500 moles, preferably 3 to 250 moles, per mole of compound (8b). In step 3, if the reaction solution obtained in step 2 is used as compound (8b) as is, carbonate ester compound (7) may remain in the reaction solution. In this case, it is preferable to use an excess amount of water in step 3. Water can also be used as a solvent. When water is used as a solvent, in addition to the above amount, it is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of compound (8b).

[0303] The reaction temperature when compound (8b) reacts with water is usually 10°C or higher, preferably 10°C to 100°C, and more preferably 10°C to 80°C.

[0304] The reaction time is typically 0.1 to 10 hours, preferably 0.1 to 5 hours.

[0305] The solvent may or may not be used. Water can be used as a solvent, but if a solvent other than water is used, examples of such solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, acetone, and methanol. When a solvent other than water is used, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of compound (8b). Two or more solvents may be mixed and used as needed.

[0306] Step 3 may, if necessary, be carried out under an inert gas atmosphere that does not affect the reaction, such as nitrogen, argon, or helium.

[0307] The obtained compound (8a) can be purified by conventional methods such as concentration and recrystallization, but it can also be used as a raw material for manufacturing method 1 without purification.

[0308] When the compound represented by formula (9) below is used as a raw material, the compound represented by formula (8) can also be produced by the following method in addition to (step 2).

[0309] The compound represented by formula (8) can be obtained by reacting the compound represented by formula (9) with the isocyanate compound represented by formula (5) (Method B). Formula (9):

[0310] [ka]

[0311] (In the formula, A, R', n, a, R 1 , R 2 and B 1 (As defined above.) Specific examples of compounds represented by formula (9) are shown below. However, the present invention is not limited to these. In the following specific examples, Et is an ethyl group, Pr is a propyl group, i Pr represents an isopropyl group, Bu represents a butyl group, and Bnz represents a benzyl group.

[0312] [ka]

[0313] TIFF0007881582000135.tif53149

[0314] [ka]

[0315] [ka]

[0316] [ka]

[0317] [ka]

[0318] [ka]

[0319] [ka]

[0320] X, a, R 1 , R 2、 R 7 , R 10 R' is as defined above. Preferably, X(R 1 ) a is NH, N(CH 3 ) or O, R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0321] [ka]

[0322] X, a, R 1 , R 2、 R 7 , R 10 R' is as defined above. Preferably, X(R 1 ) a is NH, N(CH3) or O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0323] [ka]

[0324] X, a, R 1 , R 2 , R 10 R' is as defined above. Preferably, X(R 1 ) a is NH or N(CH3), O, and R 2 is CH2, CH2CH2, or CH2(CH2)4CH2, and R 7 is CH3 or Et, and R 10 CH3,Et, i The molecule is Pr, Bu, Bnz, or CH2CH2OCH3, and R' is H, CH3, or Et.

[0325] The compounds represented by formula (9) are preferably (9a-2-1a)~(9a-2-33a), (9b-2-1a)~(9b-2-27a), (9a-2-1b)~(9a-2-33b), (9b-2-1b)~(9b-2-27b), (9a-2-1c)~(9a-2-33c), (9b-2-1c)~(9b-2-27c), and particularly preferably (9a-2-12a) and (9b-2-10a).

[0326] The reaction typically involves using 0.5 to 10 moles, preferably 0.8 to 3 moles, of the isocyanate compound represented by formula (5) for every 1 / n mole of the compound represented by formula (9).

[0327] The reaction temperature is typically between 10°C and 100°C, or the boiling point of the solvent. Preferably, it is between 20°C and 150°C.

[0328] The reaction time is typically 1 to 20 hours, preferably 1 to 10 hours.

[0329] The solvent may or may not be used. Examples of solvents include tetrahydrofuran, ethyl acetate, acetonitrile, toluene, and acetone. When a solvent is used, the amount of solvent used is usually 100 parts by mass or less, preferably 0.1 to 50 parts by mass, per 1 part by mass of the compound represented by formula (9). Two or more solvents may be mixed and used as needed. <Blocked isocyanate composition containing a blocked isocyanate compound and an amphoteric compound represented by formula (1)> The blocked isocyanate composition of the present invention contains a blocked isocyanate compound and an amphoteric compound represented by formula (1).

[0330] This section will explain blocked isocyanate compounds.

[0331] Examples of blocked isocyanate compounds include compounds obtained by reacting an isocyanate with a blocking agent, thereby encapsulating the isocyanate groups in the isocyanate with the blocking agent. Blocked isocyanate compounds may be single compounds or mixtures of two or more types.

[0332] The isocyanates constituting the blocked isocyanate compound are not particularly limited as long as they are compounds having two or more isocyanate groups, but examples of isocyanates include the following: (i) Aliphatic isocyanates, (ii) Alicyclic isocyanates, (iii) Aromatic isocyanates, (iv) Aromatic aliphatic isocyanates, (v) A modified isocyanate formed from at least one selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, and aromatic aliphatic isocyanates.

[0333] Preferably, the modified isocyanate is formed from (i) an aliphatic isocyanate, (ii) a alicyclic isocyanate, and (v) at least one selected from the group consisting of aliphatic isocyanates, alicyclic isocyanates, aromatic isocyanates, and aromatic fatty lyisocyanates.

[0334] These isocyanates may be used individually or as a mixture of two or more.

[0335] Examples of aliphatic isocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate.

[0336] Examples of alicyclic isocyanates include 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate (IPDI)), bis-(4-isocyanatocyclohexyl)methane, and norbornane diisocyanate.

[0337] Examples of aromatic isocyanates include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1,4-phenylenediisocyanate, 2,4-tolinediisocyanate, 2,6-tolinediisocyanate, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylenediisocyanate.

[0338] Examples of aromatic aliphatic isocyanates include 1,3-xylylenediisocyanate, 1,4-xylylenediisocyanate, and α,α,α',α'-tetramethylxylylenediisocyanate.

[0339] Examples of modified isocyanates include isocyanate-terminated compounds and / or reaction products of the isocyanate-terminated compounds obtained by the reaction of the above-mentioned isocyanate compound with a compound having an active hydrogen group (for example, adduct-type isocyanates, isocyanate modified products obtained by allophanate reaction, carbodiimide reaction, uretdione reaction, isocyanurate reaction, uretonimination reaction, biuret reaction, etc.), with adduct-type isocyanates, isocyanates modified by isocyanurate reaction, and isocyanates modified by biuret reaction (isocyanates having biuret bonds) being preferred.

[0340] Isocyanates containing biuret bonds are obtained by reacting an isocyanate with a so-called biuretizing agent such as water, tert-butanol, or urea, in a molar ratio of isocyanate groups between the biuretizing agent and the isocyanate, at a ratio of approximately 1 / 2 to 1 / 100, followed by removal of unreacted isocyanate and purification. Isocyanates containing isocyanurate bonds are obtained, for example, by carrying out a cyclic trimerization reaction using a catalyst, stopping the reaction when the conversion rate reaches approximately 5 to 80% by mass, and then removing unreacted isocyanate and purification. In this process, 1-6 valent alcohol compounds can be used in combination.

[0341] Examples of isocyanates containing biuret bonds include the biuret-modified 1,6-hexamethylene diisocyanate (HDI), the biuret-modified isophorone diisocyanate (IPDI), and the biuret-modified toluene diisocyanate (TDI), as shown below. Commercially available products include Desmodule N75, Desmodule N100, and Desmodule N3200 from Sumika Covestro Urethane Co., Ltd., and Duranate 24A-100, Duranate 22A-75P, and Duranate 21S-75E from Asahi Kasei Corporation.

[0342] [ka]

[0343] Isocyanates containing isocyanurate bonds can be obtained, for example, by carrying out an isocyanuration reaction using a catalyst, stopping the reaction when the conversion rate reaches approximately 5 to 80% by mass, and then removing and purifying the unreacted isocyanate. Alcohol compounds with 1 to 6 valent values ​​can be used in combination during this process.

[0344] As a catalyst for the above isocyanurate reaction, a catalyst that is generally basic is preferred.

[0345] Examples of the catalysts mentioned above include: (1) Hydroxides of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, and trimethylbenzylammonium, and organic weak salts such as acetic acid and capric acid, (2) Hydroxyalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium, and organic weak salts such as acetic acid and capric acid, (3) Metal salts of alkylcarboxylic acids, such as tin, zinc, lead, (4) Metal alkoxides such as sodium and potassium, (5) Aminosilyl group-containing compounds such as hexamethyldisilazane, (6) Mannich bases, (7) Combined use of tertiary amines and epoxy compounds, (8) Phosphorus compounds such as tributylphosphine Examples include the following, and two or more types may be used in combination.

[0346] If the catalyst may adversely affect the properties of the paint or coating film, the catalyst may be neutralized with an acidic compound. Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid; sulfonic acids or their derivatives such as methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonate methyl ester, and p-toluenesulfonate ethyl ester; ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethyl glycol acid phosphate, butyl pyrophosphate, and butyl phosphate, and two or more may be used in combination.

[0347] Examples of isocyanates having isocyanurate bonds include isocyanurate modified forms of HDI, IPDI, and TDI having the structures shown below. Commercially available products include Sumijool N3300, Desmodule 3900, Desmodule Z4470BA, Desmodule XP2763, Desmodule IL1351BA, and Desmodule HLBA from Sumika Covestro Urethane Co., Ltd., and Duranate TPA-100, Duranate MFA-75B, Duranate TUL-100, and Duranate TSA-100 from Asahi Kasei Corporation.

[0348] [ka]

[0349] Isocyanates containing urethane bonds can be obtained, for example, by reacting a diisocyanate with a divalent to hexavalent alcohol compound such as trimethylolpropane (hereinafter referred to as TMP) in a molar ratio of hydroxyl groups of the alcohol compound to isocyanate groups of the isocyanate compound of approximately 1 / 2 to approximately 1 / 100, and then removing and purifying the unreacted isocyanate. Removal and purification of unreacted isocyanates is not always necessary.

[0350] Examples of isocyanates having urethane bonds include the reaction products of HDI and TMP, IPDI and TMP, and TDI and TMP having the structures shown below. Commercially available products include Sumijoule HT, Desmodule L75(C), Desmodule UltraL75, and Desmodule L67BA from Sumika Covestro Urethane Co., Ltd., and Duranate P301-75E, Duranate AE700-100, Duranate E402-80B, and Duranate E405-70B from Asahi Kasei Corporation.

[0351] [ka]

[0352] Known blocking agents for isocyanates in which a portion of the isocyanate groups of the above-mentioned isocyanates or the modified isocyanates are encapsulated with known blocking agents include, for example, phenols such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and dieth Examples include alcohols such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; pyrazoles such as 3,5-dimethylpyrazole and 1,2-pyrazole; triazoles such as 1,2,4-triazole; halogen-substituted alcohols such as ethylene chlorhydrin and 1,3-dichloro-2-propanol; lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propyllactam; and active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate. Other examples include amines, imides, mercaptans, imines, ureas, diaryls, and the like.

[0353] Examples of blocking agents include alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds. Alcohol compounds, lactam compounds, oxime compounds, and pyrazole compounds are preferred, and alcohol compounds are particularly preferred because, when combined with the amphoteric compound represented by formula (1), the blocking agent can be dissociated in a short time even at 120°C.

[0354] Examples of alcohol compounds include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol. Alcohol compounds also include fluorinated alcohol compounds such as 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol. The alcohol compound is preferably a fluorinated alcohol compound, and particularly preferably 2,2,2-trifluoroethanol.

[0355] Examples of phenolic compounds include phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol 2-hydroxypyridine.

[0356] Examples of amine compounds include diisopropylamine.

[0357] Examples of lactam compounds include ε-caprolactam, δ-valerolactam, and γ-butyrolactam, with ε-caprolactam being preferred.

[0358] Examples of oxime compounds include those represented by the following formula (L). Formula (L): HO-N=R'' (L) (In the formula, R'' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0359] Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, 1-methylpropyl, pentyl, hexyl, heptyl, octyl, 1-ethylpentyl, nonyl, 2-ethylhexyl, undecyl, tridecyl, pentadecyl, and heptadecyl groups.

[0360] Examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, and methyl isobutyl ketoxime, with methyl ethyl ketoxime being preferred.

[0361] Examples of pyrazole compounds include 1,2-pyrazole and 3,5-dimethylpyrazole, and examples of triazole compounds include 1,2,4-triazole, with 3,5-dimethylpyrazole being preferred.

[0362] Examples of active methylene compounds include methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate.

[0363] In the blocked isocyanate composition of the present invention, known catalysts, additives, pigments, solvents, etc., commonly used in the art for polyurethane production may be used as needed.

[0364] The known catalysts for polyurethane production are not particularly limited, and include, for example, tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octoate, tin laurate, bismuth compounds such as bismuth octoate, bismuth naphthenate, bismuth acetylacetonate, tetra-n-butyl titanate, tetraisopropyl titanate, Titanium compounds such as titanium terephthalate, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,4-diazabicyclo[2.2.2]octane(D Examples include tertiary amine compounds such as ABCO), 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; and quaternary ammonium organic acid salts such as tetramethylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium forate, and 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

[0365] The additives are not particularly limited, but include, for example, UV absorbers such as hindered amines, benzotriazoles, and benzophenones; color inhibitors such as perchlorates and hydroxylamines; antioxidants such as hindered phenols, phosphorus, sulfur, and hydrazides; urethane catalysts such as tin, zinc, and amines; and other leveling agents, rheology control agents, and pigment dispersants.

[0366] The pigments are not particularly limited and include, for example, organic pigments such as quinacridone, azo, and phthalocyanine pigments; inorganic pigments such as titanium dioxide, barium sulfate, calcium carbonate, and silica; and other pigments such as carbon-based pigments, metallic foil pigments, and rust-preventive pigments.

[0367] The solvents are not particularly limited and include, for example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin; and water. These solvents may be used individually or in combination of two or more.

[0368] The thermosetting resin composition of the present invention will now be described.

[0369] The thermosetting resin composition of the present invention comprises the blocked isocyanate composition of the present invention and a compound having an isocyanate-reactive group.

[0370] Compounds having isocyanate-reactive groups include compounds having two or more active hydrogen groups, such as polyols, polyamines, and alkanolamines, with polyols being preferred. These compounds having isocyanate-reactive groups may also be a mixture of two or more types.

[0371] In the present invention, a polyol is a compound having two or more hydroxyl groups. Examples include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and fluorine polyols. Among these, acrylic polyols are preferred as polyols from the viewpoint of weather resistance, chemical resistance, and hardness. Alternatively, polyester polyols are preferred as polyols from the viewpoint of mechanical strength and oil resistance. These polyols may also be mixtures of two or more types.

[0372] Polyester polyols can be obtained, for example, by condensing a dibasic acid (either alone or a mixture of two or more) with a polyhydric alcohol (either alone or a mixture of two or more).

[0373] Examples of the aforementioned dibasic acids include succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and carboxylic acids such as 1,4-cyclohexanedicarboxylic acid.

[0374] Examples of the aforementioned polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, and ethoxylated trimethylolpropane.

[0375] A specific method for producing polyester polyols is, for example, to mix the above components and heat them at approximately 160-220°C to carry out a condensation reaction. Alternatively, polycaprolactones, such as those obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyhydric alcohol, can also be used as polyester polyols.

[0376] These polyester polyols can be modified using aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and isocyanates obtained therefrom. In particular, from the viewpoint of weather resistance and resistance to yellowing, it is preferable to modify polyester polyols using aliphatic diisocyanates, alicyclic diisocyanates, and isocyanates obtained therefrom.

[0377] When the thermosetting resin composition of this embodiment is used as a water-based paint, some carboxylic acids derived from dibasic acids, etc., in the polyester polyol are left in place and neutralized with a base such as an amine or ammonia, thereby making the polyester polyol a water-soluble or water-dispersible resin.

[0378] Examples of polyether polyols include aliphatic amine polyols, aromatic amine polyols, Mannich polyols, polyhydric alcohols, polyhydric phenols, bisphenols and other active hydrogen compounds, and compounds obtained by adding alkylene oxides to these. These polyether polyols may also be mixtures of two or more types.

[0379] Examples of aliphatic amine polyols include alkylenediamine polyols and alkanolamine polyols. These polyol compounds are polyfunctional polyol compounds with terminal hydroxyl groups obtained by ring-opening addition of at least one cyclic ether such as ethylene oxide or propylene oxide to an alkylenediamine or alkanolamine as an initiator. Known compounds can be used without limitation as alkylenediamines. Specifically, alkylenediamines with 2 to 8 carbon atoms, such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine, are preferred. These aliphatic amine polyols may also be mixtures of two or more types.

[0380] Aromatic amine polyols are polyfunctional polyether polyol compounds with terminal hydroxyl groups obtained by ring-opening and adding at least one cyclic ether such as ethylene oxide or propylene oxide to an aromatic diamine as an initiator. Any known aromatic diamine can be used as an initiator without limitation. Specifically, examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, and naphthalenediamine. Among these, the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine, or a mixture thereof) is particularly preferred. These aromatic amine polyols may also be mixtures of two or more types.

[0381] Mannich polyols are active hydrogen compounds obtained by the Mannich reaction of phenol and / or its alkyl-substituted derivatives, formaldehyde and alkanolamines, or polyol compounds obtained by ring-opening addition polymerization of these compounds with at least one of ethylene oxide or propylene oxide. These Mannich polyols may also be mixtures of two or more types.

[0382] Examples of polyhydric alcohols include dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, etc.) and trihydric or higher alcohols (e.g., glycerin, trimethylolpropane, pentaerythritol, methyl glucoside, sorbitol, sucrose, etc.). These polyhydric alcohols may also be mixtures of two or more types.

[0383] Examples of polyhydric phenols include pyrogallol and hydroquinone. These polyhydric phenols may also be a mixture of two or more types.

[0384] Examples of bisphenols include bisphenol A, bisphenol S, bisphenol F, and low-level condensates of phenol and formaldehyde. These bisphenols may also be mixtures of two or more types.

[0385] Polyether polyols can be obtained, for example, by any of the following methods (1) to (3). (1) A method for obtaining polyether polyols by randomly or block adding an alkylene oxide alone or a mixture of polyvalent hydroxy compounds alone or a mixture of polyvalent hydroxy compounds using a catalyst.

[0386] Examples of the catalysts include hydroxides (lithium, sodium, potassium, etc.), strongly basic catalysts (alkoxides, alkylamines, etc.), and complex metal cyanide compounds (metallic porphyrins, zinc hexacyanocobaltate complexes, etc.).

[0387] Examples of the alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.

[0388] (2) A method for obtaining polyether polyols by reacting a polyamine with an alkylene oxide.

[0389] Examples of the polyamines mentioned above include ethylenediamines and others, which will be discussed later.

[0390] Examples of the alkylene oxide mentioned above include those similar to those exemplified in (1).

[0391] (3) A method for obtaining so-called polymer polyols by polymerizing acrylamide or the like using polyether polyols obtained in (1) or (2) as a medium.

[0392] Examples of the aforementioned polyvalent hydroxy compounds include the following (i) to (vi):

[0393] (i) Diglycerin, ditrimethylolpropane, pentaerythritol, dipentaerythritol, etc.

[0394] (ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabinitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol.

[0395] (iii) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and ribodesose.

[0396] (iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, genthiobiose, lactose, and melibiose.

[0397] (v) Trisaccharides such as raffinose, gentianose, and meletitose.

[0398] (vi) Tetrasaccharides such as stachyose.

[0399] Acrylic polyols can be obtained, for example, by polymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule, or by copolymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule with, if necessary, another monomer copolymerizable with the polymerizable monomer.

[0400] Examples of polymerizable monomers having one or more active hydrogen atoms in a single molecule include (i) to (vi) below. These may be used individually or in combination of two or more types.

[0401] (i) Acrylic acid esters having active hydrogen, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate. (ii) Methacrylic acid esters having active hydrogen, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

[0402] (iii) (meth)acrylic acid esters having polyvalent active hydrogen, such as (meth)acrylic acid monoesters of triols like glycerin and trimethylolpropane.

[0403] (iv) Monoethers of polyether polyols (e.g., polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) and (meth)acrylic acid esters having the above-mentioned active hydrogen.

[0404] (v) Adducts of glycidyl (meth)acrylate with monobasic acids (e.g., acetic acid, propionic acid, p-tert-butylbenzoic acid, etc.).

[0405] (vi) Adducts obtained by ring-opening polymerization of lactones (e.g., ε-caprolactam, γ-valerolactone, etc.) to the active hydrogen of the above-mentioned (meth)acrylic acid esters having active hydrogen.

[0406] Other monomers copolymerizable with the polymerizable monomer include, for example, (i) to (iv) below. These may be used individually or in combination of two or more.

[0407] (i) (meth)acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, and glycidyl methacrylate.

[0408] (ii) Unsaturated amides such as acrylic acid, methacrylic acid, maleic acid, itaconic acid (unsaturated carboxylic acids such as acrylamide, N-methylolacrylamide, and diacetoneacrylamide).

[0409] (iii) Vinyl monomers having a hydrolyzable silyl group, such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acrylopropyltrimethoxysilane.

[0410] (iv) Other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0411] Specific methods for producing acrylic polyols include, for example, a method in which the above-mentioned monomer components are solution polymerized in the presence of known radical polymerization initiators such as peroxides and azo compounds, and then diluted with an organic solvent as necessary to obtain an acrylic polyol.

[0412] When the thermosetting resin composition of this embodiment is used as a water-based coating, a water-based acrylic polyol can be produced by using known methods such as solution polymerization of the above monomer components to convert them into an aqueous layer, or emulsion polymerization. In this case, the acidic portion, such as carboxylic acid-containing monomers like acrylic acid and methacrylic acid, or sulfonic acid-containing monomers, can be neutralized with amines or ammonia to impart water-soluble or water-dispersible properties to the acrylic polyol.

[0413] Examples of polyolefin polyols include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, and hydrogenated polyisoprene having two or more hydroxyl groups.

[0414] Furthermore, in polyolefin polyols, the number of hydroxyl groups is preferably three, as this allows for higher coating film strength.

[0415] In this specification, "fluorinated polyol" means a polyol containing fluorine in its molecule. Specific examples of fluorinated polyols include copolymers of fluoroolefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, and vinyl monocarboxylate esters, as disclosed in Japanese Patent Publication No. 57-34107 and Japanese Patent Publication No. 61-275311, etc. Japanese Patent Publication No. 57-34107 and Japanese Patent Publication No. 61-275311 are incorporated herein by reference in their entirety.

[0416] The lower limit of the hydroxyl value of the polyol is preferably 10 mg KOH / g or more, more preferably 20 mg KOH / g or more, and even more preferably 30 mg KOH / g or more.

[0417] On the other hand, there are no specific limitations on the upper limit of the hydroxyl value of polyols; for example, it is sufficient if it is 200 mg KOH / g or less.

[0418] In other words, the hydroxyl value of the polyol is preferably 10 mg KOH / g or more and 200 mg KOH / g or less, more preferably 20 mg KOH / g or more and 200 mg KOH / g or less, and even more preferably 30 mg KOH / g or more and 200 mg KOH / g or less.

[0419] Furthermore, the acid value of the polyol is preferably 0 mg KOH / g or more and 30 mg KOH / g or less.

[0420] The hydroxyl value and acid value can be measured in accordance with JIS K1557.

[0421] The molar equivalent ratio (NCO / OH) of the isocyanate groups of the above-described blocked isocyanate composition to the hydroxyl groups of the polyol is preferably 0.2 or more and 5.0 or less, more preferably 0.4 or more and 3.0 or less, and even more preferably 0.5 or more and 2.0 or less.

[0422] The polyamine used has two or more primary or secondary amino groups in one molecule, and among these, those having three or more are preferred.

[0423] Specific examples of polyamines include diamines such as ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, and isophoronediamine; chain polyamines having three or more amino groups such as bishexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, and tetrapropylenepentamine; and cyclic polyamines such as 1,4,7,10,13,16-hexazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane.

[0424] The term "alkanolamine" refers to a compound having an amino group and a hydroxyl group in one molecule. Examples of alkanolamines include monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono-, di-(n- or iso-)propanolamine, ethylene glycol-bis-propylamine, neopentanolamine, and methylethanolamine.

[0425] The thermosetting resin composition of this embodiment may optionally contain a melamine-based curing agent such as a fully alkyl type, methylol type, or alkylamino group type alkyl.

[0426] The thermosetting resin composition of this embodiment may contain an organic solvent.

[0427] Furthermore, the compound having the isocyanate-reactive group and the blocked isocyanate composition described above may contain an organic solvent.

[0428] The organic solvent is preferably one that is compatible with the above-mentioned blocked isocyanate composition.

[0429] Examples of organic solvents include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerin; and water. These solvents may be used individually or in combination of two or more.

[0430] Furthermore, the thermosetting resin composition of this embodiment can be used as an aqueous thermosetting resin composition dissolved or dispersed in water. When the thermosetting resin composition of the present invention is used as an aqueous thermosetting resin composition, surfactants or solvents that tend to be miscible with water may be used with respect to the block isocyanate composition of the present invention in order to improve the compatibility of the thermosetting resin composition. Examples of surfactants include anionic surfactants such as aliphatic soaps, rosinate soaps, alkyl sulfonates, dialkylaryl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkylaryl sulfates, and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene oxypropylene block copolymers. Solvents that tend to be miscible with water include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butyl glycol, N-methylpyrrolidone, butyl diglycol, or butyl diglycol acetate.

[0431] Among the above solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutanol, butyl glycol, N-methylpyrrolidone, and butyl diglycol are preferred, and diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, and dipropylene glycol dimethyl ether are more preferred. These solvents may be used individually or in combination of two or more. Furthermore, ester solvents such as ethyl acetate, n-butyl acetate, and cellosolve acetate are undesirable because the solvents themselves may undergo hydrolysis during storage.

[0432] In the thermosetting resin composition of the present invention, the blending ratio of the blocked isocyanate composition and the compound having an isocyanate-reactive group is determined by the required physical properties and is not particularly limited. Typically, the ratio of [amount of active isocyanate groups of the blocked isocyanate compound in the blocked isocyanate composition (mol)] / [amount of active hydrogen groups of the compound having an isocyanate-reactive group (mol)] is in the range of 0.2 to 5, and preferably in the range of 0.5 to 3. The effective isocyanate group of the blocked isocyanate compound refers to the isocyanate group that is regenerated when the blocking agent is dissociated from the blocked isocyanate compound.

[0433] In the thermosetting resin composition of the present invention, known catalysts, additives, pigments, etc. commonly used in the art for the production of polyurethane may be used as needed, and may also be used in combination with known blocked isocyanates.

[0434] The known catalysts for polyurethane production are not particularly limited, and include, for example, tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octoate, tin laurate, bismuth compounds such as bismuth octoate, bismuth naphthenate, bismuth acetylacetonate, tetra-n-butyl titanate, tetraisopropyl titanate, Titanium compounds such as titanium terephthalate, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,4-diazabicyclo[2.2.2]octane(D Examples include tertiary amine compounds such as ABCO), 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide; and quaternary ammonium organic acid salts such as tetramethylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium forate, and 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

[0435] The additives are not particularly limited and include, for example, UV absorbers such as hindered amines, benzotriazoles, and benzophenones; color inhibitors such as perchlorates and hydroxylamines; antioxidants such as hindered phenols, phosphorus, sulfur, and hydrazides; urethane catalysts such as tin, zinc, and amines; and various other additives used in the relevant field, such as leveling agents, defoamers, rheology control agents, thixotropy imparters / thickeners, light stabilizers, plasticizers, surfactants, coupling agents, flame retardants, rust inhibitors, fluorescent whitening agents, and pigment dispersants.

[0436] The pigments are not particularly limited and include, for example, organic pigments such as quinacridone, azo, and phthalocyanine pigments; inorganic pigments such as titanium dioxide, barium sulfate, calcium carbonate, and silica; and other pigments such as carbon-based pigments, metallic foil pigments, and rust-preventive pigments.

[0437] Known blocked isocyanates include, for example, blocked isocyanates obtained by reacting an isocyanate with a known blocking agent. Known blocking agents include, for example, phenol compounds such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oxime compounds such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, t-pentanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether. Examples include alcohol compounds such as benzyl alcohol, pyrazole compounds such as 3,5-dimethylpyrazole and 1,2-pyrazole, triazole compounds such as 1,2,4-triazole, halogen-substituted alcohol compounds such as ethylene chlorhydrin and 1,3-dichloro-2-propanol, lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propyllactam, and active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate. Other examples include amine compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds.

[0438] The thermosetting resin composition of the present invention can be used in paints for automobiles, buildings, metal products such as steel furniture, woodworking products such as musical instruments, machinery and vehicles such as construction equipment, building materials such as window frames, electrical appliances such as office equipment, coatings for artificial leather and rubber rolls, inks, adhesives, sealants for electronic components, sealing materials for automobiles and buildings, molding materials for 3D printers, and the like.

[0439] Next, a method for curing the thermosetting resin composition of the present invention will be described.

[0440] In the method of the present invention, a thermosetting resin composition which is a mixture of the above-mentioned blocked isocyanate composition and a compound having an isocyanate-reactive group is heated.

[0441] The reaction temperature varies depending on the blocked isocyanate compound and the amphoteric compound (1) in the blocked isocyanate composition used, but can be approximately 60 to 250°C, preferably 80 to 200°C. The reaction time can be approximately 30 seconds to 5 hours, preferably 1 minute to 60 minutes.

[0442] The cured product of the present invention can be produced by following the curing method for the thermosetting resin composition of the present invention described above. [Examples]

[0443] The present invention will be described in more detail using manufacturing examples and embodiments, but the present invention is not limited to these embodiments. (1) Infrared spectroscopy (IR analysis) conditions Equipment: FT-IR-6600 manufactured by JASCO Corporation Measurement method: Total internal reflection (crystal: germanium) Total number of times: 16 (2) 1 H-NMR analysis conditions Equipment: Bruker AV400 Frequency: 400MHz (3) Curing temperature and time measurement conditions Equipment: Madoka Automatic Curing Time Measurement Device manufactured by Cyber ​​Co., Ltd. Stirring rod: Model number 3JC-5060W Stirring speed: rotation 100 rpm, revolution 25 rpm (4) Method for calculating solid content Approximately 1.5 g of the sample was heated at 110°C for 3 hours, and the solid content (%) of the sample was calculated from the mass before and after heating. (5) Composition of thermosetting resin composition Blocked isocyanate compounds, compounds containing isocyanate-reactive groups, and amphoteric compounds were added so that the ratio of effective NCO groups (mol): hydroxyl groups (mol): amidate groups (mol) was 1.00:0.95:0.05. Methyl isobutyl ketone was then added so that the ratio of solids (g) of the blocked isocyanate compound to solvent (g) was 1.0:1.0. Note that the solvent here includes the solvent used to dilute the blocked isocyanate compound. The effective NCO groups (mol) and hydroxyl groups (mol) were calculated using the following formula.

[0444] Effective NCO groups (mol) = Amount of blocked isocyanate charged (g) ÷ Effective NCO group content of blocked isocyanate (%) ÷ 4.202 Hydroxyl groups (mol) = Amount of polyol added (g) × Hydroxyl value of polyol (mgKOH / g) ÷ 56.1

[0445] [Manufacturing example A-1] Synthesis of [TMPACyHU] Reaction 1: Production of [TMPACyHU] [MeCO3]

[0446] [ka]

[0447] (3-aminopropyl)dimethylamine (10 g, 97.8 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a 200 ml autoclave purged with nitrogen, and methanol (50.0 g) was added and stirred until dissolved. To the resulting mixed solution, cyclohexyl isocyanate (12.25 g, 97.4 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 25°C. Dimethyl carbonate (13.22 g, 146 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the mixed solution after the dropwise addition, and the mixture was heated at 120°C for 8 hours. After the reaction mixture was cooled to 25°C, it was concentrated under reduced pressure at 60°C for 1 hour to obtain the concentrated residue [TMPACyHU][MeCO3] represented by the above formula.

[0448] The compound represented by the above formula 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR (DMSO-d 6 )δ(ppm)=3.68(s, 3H), 3.38-3.30(m, 3H), 3.08-3.00(m, 11H), 1.87-1.43(m, 7H), 1.23-1.04(m, 5H)

[0449] Reaction 2: Production of [TMPACyHU] [HCO3]

[0450] [ka]

[0451] Water (100g) was added to the concentrated residue obtained in reaction 1 and stirred. The reaction mixture was then concentrated to obtain the concentrated residue [TMPACyHU][HCO3]. The compound represented by the above formula 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR (DMSO-d 6 )δ(ppm)=3.39-3.30(m, 3H), 3.07-2.99(m, 11H), 1.82-1.49(m, 7H), 1.24-1.04(m, 5H)

[0452] Reaction 3: Production of [TMPACyHU]

[0453] [ka]

[0454] Methanol (50g) was added to the concentrated residue obtained in reaction 2, and the mixture was heated at 60°C for 16 hours to obtain a mixture. The heated mixture was cooled to 25°C, and concentrated under reduced pressure at 60°C for 1 hour to obtain 28.2g of [TMPACyHU] represented by the above formula (yield quant.). 1 The results of the 1H-NMR analysis are shown below. 1H-NMR(MeOD)δ(ppm)=3.43-3.00(m, 13H), 1.88(br, 3H), 1.77(br, 2H), 1.63(br, 2H), 1.51(br, 1H), 1.25(br, 2H), 1.10(br, 3H)

[0455] [Manufacturing Example A-2] Synthesis of [DTMPAHDU] Reaction 1: Production of [DTMPAHDU] [MeCO3]

[0456] [ka]

[0457] (3-aminopropyl)dimethylamine (5.03 g, 49.2 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into a 200 ml autoclave purged with nitrogen, and toluene (50.0 g) was added and stirred to dissolve. To the resulting mixture, hexamethylene diisocyanate (4.12 g, 24.4 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise at 25°C and stirred. Dimethyl carbonate (13.2 g, 147 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the stirred mixture and heated at 120°C for 8 hours. After the reaction mixture was cooled to 25°C, it was concentrated under reduced pressure at 60°C for 1 hour to obtain the concentration residue [DTMPAHDU][MeCO3].

[0458] Reaction 2: Production of [DTMPAHDU][HCO3]

[0459] [ka]

[0460] Water (100g) was added to the reaction residue obtained in Reaction 1 and stirred for 1 hour to obtain a mixture. The mixture was then concentrated under reduced pressure at 60°C for 1 hour to obtain the concentrated residue [DTMPAHDU][HCO3] represented by the above formula.

[0461] Reaction 3: Production of [DTMPAHDU]

[0462] [ka]

[0463] Toluene (30g) was added to the concentrated residue obtained in Reaction 2, and the mixture was heated at 60°C for 3 hours to obtain a mixed solution. The heated mixture was cooled to 25°C, and concentrated under reduced pressure at 60°C for 1 hour to obtain 10.5g of [DTMPAHDU] represented by the above formula (yield quant.). 1 The results of the 1H-NMR analysis are shown below. 1 H-NMR(MeOD)δ(ppm)=3.36-3.28(m, 4H), 3.04-3.03(m, 22H), 2.94-2.92(t, J=6.4Hz, 4H), 1.82-1.78(m, 4H), 1.36-1.22(m, 8H)

[0464] Manufacturing method for [Manufacturing Example A-3] [TMPADBHDIU] Reaction 1: Production of [TMPADBHDIU][MeCO3]

[0465] [ka]

[0466] (In the formula, R i , R ii Of these, at least one is substituted with the group represented by (Q1'), and the rest are substituted with the group represented by (Q2). i , R ii Compounds in which all are substituted with groups represented by (Q1'), or R i , R ii The reaction mixture may contain compounds in which all of the groups represented by (Q2) are substituted.

[0467] In a nitrogen-purged 200 ml cylindrical flask, hexamethylene diisocyanate (50.0 g, 297 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in methanol (50.1 g). Dibutylamine (38.3 g, 296 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resulting mixture over 1 hour at 25-75°C. Next, (3-aminopropyl)dimethylamine (30.3 g, 297 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour at 25-75°C. The reaction mixture was stirred at 25-75°C for 1 hour. The resulting reaction mixture was added to a 500 ml autoclave. Dimethyl carbonate (40.0 g, 445 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was reacted at 120°C for 6 hours. The resulting reaction solution was concentrated under reduced pressure at 60°C for 1 hour, and the concentrated residue was obtained as [TMPADBHDIU][MeCO3], which is presumed to be a mixture of compounds represented by the above formula.

[0468] Reaction 2: Production of [TMPADBHDIU]

[0469] [ka]

[0470] (In the formula, R i , R ii Of these, at least one is substituted with the group represented by (Q1), and the rest are substituted with the group represented by (Q2). i , R ii Compounds in which all are substituted with groups represented by (Q1), or R i , R ii The reaction mixture may contain compounds in which all of the groups represented by (Q2) are substituted.

[0471] The concentrated residue obtained in Reaction 1 was dissolved in toluene (100 g) and reacted under reflux conditions for 3 hours. The mixture was concentrated under reduced pressure at 60°C to obtain 134.2 g (yield quant.) of the mixture represented by the above formula [TMPADBHDIU]. The ratio of (Q1) groups to (Q2) groups in this mixture is 1:1. [TMPADBHDIU] is presumed to be a mixture of compounds represented by the above formula. 1 Figure 1 shows the results of the 1H-NMR (DMSO-d6) analysis, and Figure 2 shows the results of the IR analysis.

[0472] Manufacturing method for [Manufacturing Example A-4] [TMPADBcrMDIU] Reaction 1: Production of [TMPADBcrMDIU][MeCO3]

[0473] [ka]

[0474] (In the formula, R iii , R iv , R v Of these, at least one is substituted with the group represented by (Q3), and the rest are substituted with the group represented by (Q4'). iii , R iv , R v Compounds in which all are substituted with groups represented by (Q3), or R iii , R iv , R v The reaction mixture may contain compounds in which all groups are substituted with groups represented by (Q4'). (m is an integer between 0 and 4.)

[0475] In a nitrogen-purged 200 ml cylindrical flask, toluene (50 g) was added to crMDI (25.0 g, NCO group content: 31.0 (%)) (Sumijoule 44V 20 L, manufactured by Sumika Covestro Urethane Co., Ltd.) and dissolved. Dibutylamine (14.2 g, 109 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resulting mixture over 25-45°C for 1 hour, followed by the dropwise addition of (3-aminopropyl)dimethylamine (7.68 g, 75.1 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) over 25-45°C for 1 hour. The reaction mixture was stirred at 25-45°C for 1 hour. The resulting reaction mixture was concentrated under reduced pressure at 60°C for 1 hour. The resulting concentrate was added to a 180 ml autoclave, dissolved in methanol (20.3 g), and dimethyl carbonate (40.77 g, 451 mmol) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. This mixture was reacted at 125°C for 8 hours. The resulting reaction solution was concentrated under reduced pressure at 60°C for 1 hour to obtain the concentrated residue [TMPADBcrMDIU][MeCO3].

[0476] Reaction 2: Production of [TMPADBcrMDIU]

[0477] [ka]

[0478] (In the formula, R iii , R iv , R v Of these, at least one is substituted with the group represented by (Q3), and the rest are substituted with the group represented by (Q4). iii , R iv , R v Compounds in which all are substituted with groups represented by (Q3), or R iii , R iv , R v The reaction mixture may contain compounds in which all of the groups are substituted with groups represented by (Q4). (m is an integer between 0 and 4.)

[0479] The concentrated residue obtained in Reaction 1 was dissolved in methanol (60 g) and reacted under reflux conditions for 5 hours. The mixture was concentrated under reduced pressure at 60°C to obtain 55.96 g (yield quant.) of [TMPADBcrMDIU] represented by the above formula. The ratio of (C) groups to (D) groups in this mixture is 3:2. It is presumed to be a mixture of compounds represented by the above formula. 1 The results of the 1H-NMR (DMSO-d6) analysis are shown in Figure 3, and the results of the IR analysis are shown in Figure 4.

[0480] [Production Example B-1] Synthesis of trifluoroethanol block of biuret-type HDI In a nitrogen-purged 200 mL three-neck reactor, 150.0 g of biuret-type HDI (Desmodule N3200A, NCO group content: 22.8 (%), manufactured by Sumika Covestro Urethane Co., Ltd.) (NCO group: 0.81 mol) and 73.3 g of methyl isobutyl ketone (hereinafter referred to as MIBK) were charged, and the temperature was raised to 65°C. Then, 1.4 g of triethylamine (hereinafter referred to as TEA) was added. Subsequently, 27.0 g (0.99 mol) of 2,2,2-trifluoroethanol (hereinafter referred to as TFE) and 79.4 g of MIBK were added dropwise to the reaction vessel, and the mixture was stirred at 65°C for 2 hours. Infrared spectroscopy analysis revealed that the isocyanate group was at 2270 cm⁻¹. -1 The disappearance of the infrared absorption peak in the vicinity was confirmed. The obtained reaction solution was concentrated under reduced pressure, and after removing the TEA and most of the MIBK, 59.9 g of MIBK was added to obtain 306.1 g of MIBK solution of biuret-type HDI TFE block bodies. The solid content of the obtained biuret-type HDI TFE block bodies was 76.1%, and the effective NCO group content was 11.2%.

[0481] [Example 1] A thermosetting resin composition was prepared by adding the TFE block of biuret-type HDI obtained in Production Example B-1, polyester polyol (P-510, manufactured by Kuraray Co., Ltd.), and the blocking agent dissociation catalyst [TMPACyHU] obtained in Production Example A-1, and stirring for 30 minutes, so that the composition of the thermosetting composition was effective NCO groups (mol): hydroxyl groups (mol): curing catalyst (mol) = 1.00:0.95:0.05.

[0482] Approximately 0.6 mL of the prepared thermosetting resin composition was poured onto a hot plate of an automatic curing time measuring device heated to 120°C and stirred. The curing time was measured and evaluated, with the time taken from when the stirring torque was less than 1% (0.04 mN·m) immediately after stirring began until it exceeded 50% (0.86 mN·m) being defined as the curing time. The results are shown in Table 1.

[0483] [Examples 2, 3, 4, Comparative Example 1] A thermosetting composition was prepared in the same manner as in Example 1, except that the blocking agent dissociation catalyst was changed to one shown in Table 1. The curing time was then measured and evaluated. The results are shown in Table 1.

[0484] [Table 1]

Claims

1. A blocking agent dissociation catalyst for blocked isocyanates containing an amphoteric compound represented by the following formula (1). Formula (1): 【Chemistry 1】 (In the formula, R １ represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. If X is a nitrogen atom, a represents 1; if X is an oxygen atom, a represents 0. R ２ represents a substituted or unsubstituted divalent hydrocarbon group. B １ (where n is an integer of 1 or more, and A is an n-valent substituted or unsubstituted hydrocarbon group.) Formula (2): 【Chemistry 2】 (where Y ＋ represents a nitrogen cation. R ３ , R ４ and R ５ are the same or different and represent a substituted or unsubstituted hydrocarbon group. Also, R ３ , R ４ and R ５ may be partially or wholly bonded to each other to form a ring structure.) Formula (3): 【Transformation 3】 (In the formula, R ８ R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ R represents a substituted or unsubstituted hydrocarbon group having a bond with the following: ６ , R ７ , and R ９ They are the same or different, R ２ A bond with, a substituted or unsubstituted hydrocarbon group or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ６ , R ７ , R ８ , and R ９ One of the following is R ２ A joint or R ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ６ , R ７ , R ８ and R ９ These may be partially or entirely bonded to each other to form a ring structure. ６ , R ７ , R ８ and R ９ When some or all of them are bonded to each other to form a ring structure, R ６ , R ７ , R ８ and R ９ Of these, the group that does not form the ring structure is R ２ A joint or R ２ If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R ２ It has a bonding hand that connects to Z. ＋ (This indicates a nitrogen cation.)

2. Y ＋ The blocking agent dissociation catalyst for blocked isocyanates according to claim 1, wherein is a nitrogen cation, or the cationic group represented by formula (3) is a group represented by formula (3-1), formula (3-2), formula (3-1a), or formula (3-2a). Formula (3-1): 【Chemistry 4】 (R ７ is R ２ A bond with, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ８ , R １０ , R １１ and R １２ They are the same or different, R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ７ , R ８ , R １０ , R １１ and R １２ One of the following is R ２ A coupling or R that connects to it ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ７ , R ８ , R １０ , R １１ and R １２ (If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure.) Formula (3-2): 【Transformation 5】 (R ７ is R ２ A bond with, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ８ , R １３ , R １４ , R １５ and R １６ They are the same or different, R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ７ , R ８ , R １３ , R １４ , R １５ and R １６ One of the following is R ２ A coupling or R that connects to it ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ７ , R ８ , R １３ , R １４ , R １５ and R １６ (If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure.) Formula (3-1a), formula (3-2a): 【Transformation 6】 (wherein, R ７ , R ８ , R １０ , R １３ and R １４ are as defined above. R ｗ , R ｘ , R ｙ and R ｚ each represent a bond with R ２ , a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.).

3. The blocking agent dissociation catalyst for blocked isocyanates according to claim 1 or 2, wherein A is any of the following: an n-valent substituted or unsubstituted aliphatic hydrocarbon group, an n-valent substituted or unsubstituted alicyclic hydrocarbon group, an n-valent substituted or unsubstituted aromatic hydrocarbon group, or an n-valent substituted or unsubstituted aromatic aliphatic hydrocarbon group.

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

5. The blocking agent dissociation catalyst for blocked isocyanates according to claim 1 or 2, wherein X is a nitrogen atom.

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

7. The blocked isocyanate composition according to claim 6, wherein the blocked isocyanate compound is blocked with at least one blocking agent selected from the group consisting of alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, ketoenol compounds, active methylene compounds, pyrazole compounds, triazole compounds, imide compounds, mercaptan compounds, imine compounds, urea compounds, and diaryl compounds.

8. The blocked isocyanate composition according to claim 6, wherein the blocked isocyanate compound is a blocked isocyanate compound blocked with a fluorine alcohol compound.

9. A thermosetting resin composition comprising the blocked isocyanate composition according to claim 6 and a compound having an isocyanate-reactive group.

10. The thermosetting resin composition according to claim 9, wherein the compound having an isocyanate reactive group is a polyol compound.

11. A cured product obtained by curing the thermosetting resin composition described in claim 9.

12. A method for producing a cured product, comprising the step of heating and curing the thermosetting resin composition described in claim 9.

13. An amphoteric compound represented by the following formula (1). Formula (1): 【Transformation 7】 (In the formula, R １ represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. When X is a nitrogen atom, a represents 1, and when X is an oxygen atom, a represents 0. R ２ represents a substituted or unsubstituted divalent hydrocarbon group. B １ represents a cationic group represented by formula (2) or formula (3). n is an integer of 1 or more. A represents an n-valent substituted or unsubstituted hydrocarbon group.) Formula (2): 【Transformation 8】 (In the formula, Y ＋ R represents a nitrogen cation. ３ , R ４ and R ５ R represents the same or different substituted or unsubstituted hydrocarbon groups. ３ , R ４ and R ５ (Some or all of these may be bonded to each other to form a ring structure.) Formula (3): 【Chemistry 9】 (In the formula, R ８ R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ A substituted or unsubstituted hydrocarbon group having a bond with R ６ , R ７ and R ９ They are the same or different, R ２ A bond with, a substituted or unsubstituted hydrocarbon group or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ６ , R ７ , R ８ , and R ９ One of the following is R ２ A joint or R ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ６ , R ７ , R ８ and R ９ These may be partially or entirely bonded to each other to form a ring structure. ６ , R ７ , R ８ and R ９ When some or all of them are bonded to each other to form a ring structure, R ６ , R ７ , R ８ and R ９ Of these, the group that does not form the ring structure is R ２ A joint or R ２ If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R ２ It has a bonding hand that connects to Z. ＋ (This indicates a nitrogen cation.)

14. Y ＋ The amphoteric compound according to claim 13, wherein is a nitrogen cation, or the cationic group represented by formula (3) is a group represented by formula (3-1), formula (3-2), formula (3-1a), or formula (3-2a). Formula (3-1): 【Chemistry 10】 (R ７ is R ２ A bond with, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ８ , R １０ , R １１ and R １２ They are the same or different, R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ７ , R ８ , R １０ , R １１ and R １２ One of the following is R ２ A coupling or R that connects to it ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ７ , R ８ , R １０ , R １１ and R １２ (If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure.) Formula (3-2): 【Chemistry 11】 (R ７ is R ２ A bond with, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ８ , R １３ , R １４ , R １５ and R １６ They are the same or different, R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ７ , R ８ , R １３ , R １４ , R １５ and R １６ One of the following is R ２ A coupling or R that connects to it ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ７ , R ８ , R １３ , R １４ , R １５ and R １６ (If the group is a substituted or unsubstituted hydrocarbon group, some or all of them may bond to each other to form a ring structure.) Formula (3-1a), formula (3-2a): 【Chemistry 12】 (In the formula, R ７ , R ８ , R １０ , R １３ and R １４ This is as defined above. R ｗ , R ｘ , R ｙ and R ｚ These are R ２ (This indicates a bond with a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

15. The amphoteric compound according to claim 13 or 14, wherein A is any of the following: an n-valent substituted or unsubstituted aliphatic hydrocarbon group, an n-valent substituted or unsubstituted alicyclic hydrocarbon group, an n-valent substituted or unsubstituted aromatic hydrocarbon group, or an n-valent substituted or unsubstituted aromatic aliphatic hydrocarbon group.

16. The amphoteric compound according to claim 13 or 14, wherein n is 1 to 20.

17. The amphoteric compound according to claim 13 or 14, wherein X is a nitrogen atom.

18. R ２ The amphoteric compound according to claim 13 or 14, wherein the group is a substituted or unsubstituted divalent alkylene group.

19. A method for producing an amphoteric compound represented by formula (1), comprising stirring the compound represented by formula (8) in a solvent. 【Chemistry 13】 (In the formula, R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.) R １ represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. If X is a nitrogen atom, a represents 1; if X is an oxygen atom, a represents 0. R ２ represents a substituted or unsubstituted divalent hydrocarbon group. B １ (where n is an integer of 1 or more, and A is an n-valent substituted or unsubstituted hydrocarbon group.) Formula (2): 【Chemistry 14】 (In the formula, Y ＋ R represents a nitrogen cation. ３ , R ４ and R ５ R represents the same or different substituted or unsubstituted hydrocarbon groups. ３ , R ４ and R ５ (Some or all of these may be bonded to each other to form a ring structure.) Formula (3): 【Chemistry 15】 (In the formula, R ８ R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ R represents a substituted or unsubstituted hydrocarbon group having a bond with the following: ６ , R ７ , and R ９ They are the same or different, R ２ A bond with, a substituted or unsubstituted hydrocarbon group or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ６ , R ７ , R ８ , and R ９ One of the following is R ２ A joint or R ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ６ , R ７ , R ８ and R ９ These may be partially or entirely bonded to each other to form a ring structure. ６ , R ７ , R ８ and R ９ When some or all of them are bonded to each other to form a ring structure, R ６ , R ７ , R ８ and R ９ Of these, the group that does not form the ring structure is R ２ A joint or R ２ If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R ２ It has a bonding hand that connects to Z. ＋ (This indicates a nitrogen cation.)

20. The method according to claim 19, further comprising the step of reacting a compound represented by formula (6) with a carbonate ester compound represented by formula (7a) or formula (7b) to produce a compound represented by formula (8). 【Chemistry 16】 (In the formula, B １ｘ B is a group represented by the following formula (10) or formula (11). １ｘ The following formula In the case of the group represented by (10), use the carbonate ester compound represented by formula (7a), B １ｘ If the group is represented by formula (11) below, the carbonate ester compound represented by formula (7b) is used. R' is a hydrogen atom or a substituted or unsubstituted hydrocarbon group, R ３ or R ７ This indicates R ３ R indicates a substituted or unsubstituted hydrocarbon group. ７ This indicates a substituted or unsubstituted hydrocarbon group. R １ , R ２ , B 1 (A, a, X, and n are as defined above.) Formula (10): 【Chemistry 17】 (In the formula, Y represents a nitrogen atom. R ４ and R ５ (As defined above.) Formula (11): [Chemistry 18] (In the formula, Z represents a nitrogen atom. R ６ , R ８ and R ９ (As defined above.)

21. A compound represented by the following formula (8). 【Chemistry 19】 (In the formula, R' represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group. １ represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group. X represents a nitrogen atom or an oxygen atom. a represents 0 or 1. If X is a nitrogen atom, a represents 1; if X is an oxygen atom, a represents 0. R ２ represents a substituted or unsubstituted divalent hydrocarbon group. B １ (where n is an integer of 1 or more, and A is an n-valent substituted or unsubstituted hydrocarbon group.) Formula (2): 【Chemistry 20】 (In the formula, Y ＋ R represents a nitrogen cation. ３ , R ４ and R ５ R represents the same or different substituted or unsubstituted hydrocarbon groups. ３ , R ４ and R ５ (Some or all of these may be bonded to each other to form a ring structure.) Formula (3): 【Chemistry 21】 (In the formula, R ８ R ２ A bond with, a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or R ２ A substituted or unsubstituted hydrocarbon group having a bond with R ６ , R ７ and R ９ They are the same or different, R ２ A bond with, a substituted or unsubstituted hydrocarbon group or R ２ R indicates a substituted or unsubstituted hydrocarbon group having a bond with . ６ , R ７ , R ８ , and R ９ One of the following is R ２ A joint or R ２ It becomes a substituted or unsubstituted hydrocarbon group having a bond with R. ６ , R ７ , R ８ and R ９ These may be partially or entirely bonded to each other to form a ring structure. ６ , R ７ , R ８ and R ９ When some or all of them are bonded to each other to form a ring structure, R ６ , R ７ , R ８ and R ９ Of these, the group that does not form the ring structure is R ２ A joint or R ２ If it is not a substituted or unsubstituted hydrocarbon group having a bond with R, then one of the ring structures is R ２ It has a bonding hand that connects to Z. ＋ (This indicates a nitrogen cation.)

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