Amidate compound and its production method, blocking agent dissociation catalyst, and thermosetting resin composition

Abstract

The present invention provides a method for producing an amidate compound represented by formula (3) (wherein y, z, A, and R1 to R5 are as defined in the description), the method comprising a step in which an imidazoliumcarboxylic acid salt represented by formula (1) (wherein R1 to R5 are as defined in the description) is reacted with a polyisocyanate compound represented by formula (2) (wherein A and x are as defined in the description).

Description

[Technical Field]

[0001] The present invention relates to an amidate compound, a method for producing the same, a blocking agent dissociation catalyst, and a thermosetting resin composition. [Background technology]

[0002] A known conventional method for producing an amidate compound is to react an N-heterocyclic carbene (hereinafter referred to as an NHC carbene) with an isocyanate (Non-Patent Document 1).

[0003] Patent Document 1 discloses an amidate compound that can be used as a blocking agent dissociation catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2019065953A1 [Non-patent literature]

[0005] [Non-Patent Document 1] Struct.Chem. 2013, Vol. 24, pp. 2059-2068 Summary of the Invention [Problem to be solved by the invention]

[0006] In the method of reacting an NHC carbene with an isocyanate described in Non-Patent Document 1, it is necessary to use an NHC carbene that is generally unstable to oxygen and water, and therefore production must be carried out under water- and oxygen-free conditions using special equipment such as a glove box.

[0007] An object of the present invention is to provide a method for producing an amidate compound that does not require special equipment such as a glove box. [Means for solving the problem]

[0008] The present invention provides the following amidate compound, a method for producing the same, a blocking agent dissociation catalyst, and a thermosetting resin composition. [1] The following formula (1)

[0009] [ka]

[0010] (In the formula, R 1 and R 4 R may be the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom. 2 and R 3 are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a hetero atom, or R 2 and R 3 may form a ring structure together with the carbon atom to which they are attached. 5 represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a heteroatom. and an imidazolium carboxylate represented by the following formula (2):

[0011] [ka]

[0012] (In the formula, A represents a residue obtained by removing an isocyanate group from at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates, or a residue obtained by removing an isocyanate group from a modified isocyanate formed from at least one polyisocyanate selected from the group consisting of aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates; and x represents an integer of 2 or more and 20 or less.) The method includes a step of reacting a polyisocyanate compound represented by the following formula (3):

[0013] [ka]

[0014] (In the formula, y and z are integers of 1 or more and 19 or less, and the sum of y and z is 2 or more and 20 or less. A, R 1 , R 2 , R 3 , R 4 , R 5 are each as defined above.) A method for producing an amidate compound represented by the formula: [2] The method for producing an amidate compound according to [1], wherein the polyisocyanate compound represented by formula (2) is an aromatic polyisocyanate. [3] The method for producing an amidate compound according to [1], wherein the polyisocyanate compound represented by formula (2) is a dimeric or trimeric polyisocyanate formed from one or more members selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate. [4] The method for producing an amidate compound according to [1], wherein the polyisocyanate compound represented by formula (2) is at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate. [5] R 2 and R 3 The method for producing an amidate compound according to any one of [1] to [4], wherein is a hydrogen atom. [6] Formula (3)

[0015] [ka]

[0016] (In the formula, y and z are integers of 1 or more and 19 or less, and the sum of y and z is 2 or more and 20 or less. R 1 and R 4 R may be the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom. 2 and R 3 are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a hetero atom, or R 2 and R 3 may form a ring structure together with the carbon atom to which they are attached. 5 represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a heteroatom. An amidate compound represented by the formula: [7] R 2 and R 3 [6] The amidate compound according to [6], wherein [8] R 1 and R 4 is an alkyl group having 1 to 20 carbon atoms which may be substituted with a heteroatom. [9] A blocking agent dissociation catalyst for blocked isocyanates, comprising the amidate compound according to any one of [6] to [8].

[10] A thermosetting resin composition containing the amidate compound according to any one of [6] to [8], a blocked isocyanate, and a compound having an isocyanate-reactive group.

[11] A cured product obtained by curing the thermosetting resin composition according to

[10] .

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

[10] . [Effects of the Invention]

[0017] A novel method for producing an amidate compound can be provided, which does not require special equipment such as a glove box.

[0018] Furthermore, the amidate compound represented by formula (3) which can be produced by the present invention is a novel compound and is useful as a blocking agent dissociation catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0019] <Amidate Compound Represented by Formula (3) and Method for Producing the Same> In the present invention, the amidate compound represented by formula (3) (hereinafter referred to as amidate compound (3)) is produced by reacting an imidazolium carboxylate represented by formula (1) (hereinafter referred to as imidazolium carboxylate (1)) with a polyisocyanate compound represented by formula (2) (hereinafter referred to as polyisocyanate compound (2)) in the presence of a solvent, if necessary. The reaction is typically carried out by using the imidazolium carboxylate (1) and the polyisocyanate compound (2) so that c / 2a = 0.5 to 2.0, where a is the number of moles of imidazolium carboxylate (1) and c is the number of moles of isocyanate groups in the polyisocyanate compound (2). When the imidazolium carboxylate (1) is produced by the method for producing the imidazolium carboxylate (1) described below, carboxylic acid (6) may remain in the imidazolium carboxylate (1). In such a case, the imidazolium carboxylate (1) and the polyisocyanate compound (2) are used so that c / (2a+b)=0.5 to 2.0, where a is the number of moles of the imidazolium carboxylate (1), b is the number of moles of the carboxylic acid (6) remaining in the imidazolium carboxylate (1), and c is the number of moles of the isocyanate groups in the polyisocyanate compound (2).

[0020] Generally, the reaction proceeds advantageously at a reaction temperature of -10°C or higher, preferably 0 to 150°C, for a reaction time of 0.5 to 12 hours.

[0021] A solvent may or may not be used. When a solvent is used, specific examples include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic or alicyclic hydrocarbons such as methylcyclohexane, cyclohexane, hexane, heptane, and octane; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; and ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane. Of these, aromatic hydrocarbons and halogenated aromatic hydrocarbons are preferred, and toluene is particularly preferred. Two or more solvents can also be used in combination as needed.

[0022] The amount of the solvent used is usually 50 parts by mass or less, preferably 0.1 to 10 parts by mass, per part by mass of the imidazolium carboxylate (1).

[0023] If necessary, the reaction may be carried out in an inert gas atmosphere such as nitrogen, argon, or helium, which does not affect the reaction.

[0024] After the reaction is completed, the reaction mixture is concentrated or filtered to remove the solvent, thereby obtaining amidate compound (3), which may be purified, if necessary, by recrystallization or column fractionation.

[0025] In formula (1), R 1 and R 4represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom, preferably a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a heteroatom, and particularly preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a heteroatom. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 1,1,3,3-tetramethylbutyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an allyl group, a benzyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-(dimethylamino)ethyl group. Preferred are methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, benzyl, phenyl, and 2,4,6-trimethylphenyl groups, and particularly preferred are methyl, ethyl, butyl, octyl, 2-ethylhexyl, and benzyl groups.

[0026] R 1 and R 4 In the formula (I), examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, the hydrocarbon group has a group such as -O-, -N<, -S-, or -SO2-, and the hydrocarbon chain is interrupted by this group. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, it is preferred that the hydrocarbon group is substituted with an oxygen atom and the hydrocarbon chain is interrupted by an -O- group.

[0027] R 2 and R 3represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom, preferably a hydrogen atom. Furthermore, the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom is preferably a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a heteroatom, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms which may be substituted with a heteroatom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an allyl group, a benzyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-(dimethylamino)ethyl group. Preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-(dimethylamino)ethyl group, and particularly preferred are a methyl group, an ethyl group, a butyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-(dimethylamino)ethyl group.

[0028] R 2 and R 3 In the formula (I), examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, the hydrocarbon group has a group such as -O-, -N<, -S-, or -SO2-, and the hydrocarbon chain is interrupted by this group. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, it is preferred that the hydrocarbon group is substituted with an oxygen atom and the hydrocarbon chain is interrupted by an -O- group.

[0029] R 2 and R 3 may form a ring structure together with the carbon atom to which they are attached. 2 and R3 When these are taken together with the carbon atom to which they are attached to form a ring structure, they can take the form of, for example, a benzimidazolium ring structure as shown below.

[0030] [ka]

[0031] (In the formula, R 1 , R 4 and R 5 is as defined above. w , R x , R y and R z represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.) R w , R x , R y and R z Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an allyl group, a benzyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,6-diisopropylphenyl group, and a 2,4,6-trimethylphenyl group.

[0032] R 5represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a heteroatom, and is preferably a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom. The hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom is preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a heteroatom, and particularly preferably a hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a heteroatom. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 1-ethylpentyl group, a nonyl group, a 2-ethylhexyl group, an undecyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, a vinyl group, an allyl group, a benzyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2-methoxymethyl group, a 2-ethoxymethyl group, and a 2-(dimethylamino)methyl group, of which a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a heptyl group, a cyclohexyl group, a 1-ethylpentyl group, and a phenyl group are preferred, and a methyl group, an ethyl group, a heptyl group, and a 1-ethylpentyl group are particularly preferred.

[0033] R 5 In the formula (I), examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, the hydrocarbon group has a group such as -O-, -N<, -NH-, -S-, or -SO2-, and the hydrocarbon chain is interrupted by this group. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, it is preferred that the hydrocarbon group is substituted with an oxygen atom and the hydrocarbon chain is interrupted by an -O- group. In another embodiment, when a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, the hydrocarbon group may have a group such as -OH or -NH2.

[0034] Examples of the imidazolium carboxylate (1) include 1,3-dimethylimidazolium formate, 1-ethyl-3-methylimidazolium formate, 1-butyl-3-methylimidazolium formate, 1-methyl-3-octylimidazolium formate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-methyl-3-(2-ethylhexyl)imidazolium formate, 1-dodecyl-3-methylimidazolium formate, 1-methyl-3-octadecylimidazolium formate, and 1-benzyl-3-methylimidazolium formate. Salts, 1,3-dibutylimidazolium formate, 1-butyl-3-ethylimidazolium formate, 1-butyl-3-octylimidazolium formate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-butyl-3-(2-ethylhexyl)imidazolium formate, 1-butyl-3-dodecylimidazolium formate, 1-butyl-3-octadecylimidazolium formate, 1-benzyl-3-butylimidazolium formate, 1,3-dioctylimidazolium formate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium formate )imidazolium formate, 1-ethyl-3-octylimidazolium formate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-octyl-3-(2-ethylhexyl)imidazolium formate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium formate, 1-dodecyl-3-octylimidazolium formate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1-octyl-3-octadecylimidazolium formate, 1-(1,1,3,3 -tetramethylbutyl)-3-octadecylimidazolium formate, 1-benzyl-3-octylimidazolium formate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium formate, 1,3-bis(2-ethylhexyl)imidazolium formate, 1-ethyl-3-(2-ethylhexyl)imidazolium formate, 1-(2-ethylhexyl)-3-dodecylimidazolium formate, 1-(2-ethylhexyl)-3-octadecylimidazolium formate, 1-benzyl-3-(2-ethylhexyl)imidazolium formate, 1,3-Didodecylimidazolium formate, 1-dodecyl-3-octadecylimidazolium formate, 1-benzyl-3-dodecylimidazolium formate, 1,3-dioctadecylimidazolium formate, 1-benzyl-3-octadecylimidazolium formate, 1,3-dibenzylimidazolium formate;, 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-methyl-3-octylimidazolium acetate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-methyl-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-methylimidazolium acetate, 1-methyl-3-octadecylimidazolium acetate, 1-benzyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1-Butyl-3-ethylimidazolium acetate, 1-butyl-3-octylimidazolium acetate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-butyl-3-(2-ethylhexyl)imidazolium acetate, 1-butyl-3-dodecylimidazolium acetate, 1-butyl-3-octadecylimidazolium acetate, 1-benzyl-3-butylimidazolium acetate, 1,3-dioctylimidazolium acetate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate Acid salt, 1-ethyl-3-octylimidazolium acetate, 1-ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3-(2-ethylhexyl)imidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3-octadecylimidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)imidazolium acetate methylbutyl)-3-octadecylimidazolium acetate, 1-benzyl-3-octylimidazolium acetate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1,3-bis(2-ethylhexyl)imidazolium acetate, 1-ethyl-3-(2-ethylhexyl)imidazolium acetate, 1-(2-ethylhexyl)-3-dodecylimidazolium acetate, 1-(2-ethylhexyl)-3-octadecylimidazolium acetate, 1-benzyl-3-(2-ethylhexyl)imidazolium acetate, 1,3-Didodecylimidazolium acetate, 1-dodecyl-3-octadecylimidazolium acetate, 1-benzyl-3-dodecylimidazolium acetate, 1,3-dioctadecylimidazolium acetate, 1-benzyl-3-octadecylimidazolium acetate, 1,3-dibenzylimidazolium acetate; 1,3-Dimethylimidazolium 2-ethylhexanoate, 1-Ethyl-3-methylimidazolium 2-ethylhexanoate, 1-Butyl-3-methylimidazolium 2-ethylhexanoate, 1-Methyl-3-octylimidazolium 2-ethylhexanoate, 1-Methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-Methyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-Dodecyl-3-methylimidazolium 2-ethylhexanoate , 1-methyl-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-methylimidazolium 2-ethylhexanoate, 1,3-dibutylimidazolium 2-ethylhexanoate, 1-butyl-3-ethylimidazolium 2-ethylhexanoate, 1-butyl-3-octylimidazolium 2-ethylhexanoate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-butyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate 1-Butyl-3-dodecylimidazolium 2-ethylhexanoate, 1-Butyl-3-octadecylimidazolium 2-ethylhexanoate, 1-Benzyl-3-butylimidazolium 2-ethylhexanoate, 1,3-Dioctylimidazolium 2-ethylhexanoate, 1,3-Bis(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-Ethyl-3-octylimidazolium 2-ethylhexanoate, 1-Ethyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-octyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-octyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-octylimidazolium 2-ethylhexanoate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-octyl-3-octadecylimidazolium 2-ethylhexanoate, 1-(1,1,3,3-tetramethylbutyl)-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-octylimidazolium 2-ethylhexanoate, 1-benzyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1,3-bis(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-ethyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-(2-ethylhexyl)-3-dodecylimidazolium 2-ethylhexanoate, 1-(2-ethylhexyl)-3-octadecylimidazolium 2-ethylhexanoate Octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1,3-didodecylimidazolium 2-ethylhexanoate, 1-dodecyl-3-octadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-dodecylimidazolium 2-ethylhexanoate, 1,3-dioctadecylimidazolium 2-ethylhexanoate, 1-benzyl-3-octadecylimidazolium 2-ethylhexanoate, 1,3-dibenzylimidazolium 2-ethylhexanoate;, 1,3-dimethylbenzimidazolium formate, 1,3-dimethylbenzimidazolium acetate, 3-dimethylbenzimidazolium 2-ethylhexanoate;

[0035] Preferred imidazolium carboxylates (1) include 1,3-dimethylimidazolium acetate, 1-butyl-3-methylimidazolium acetate, 1-methyl-3-octylimidazolium acetate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-methyl-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-methylimidazolium acetate, 1,3-dibutylimidazolium acetate, 1-butyl-3-octylimidazolium acetate, and 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate. Imidazolium acetate, 1-butyl-3-(2-ethylhexyl)imidazolium acetate, 1-butyl-3-dodecylimidazolium acetate, 1,3-dioctylimidazolium acetate, 1-octyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1-octyl-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-octylimidazolium acetate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium acetate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl)imidazolium acetate 1-(2-ethylhexyl)-3-dodecylimidazolium acetate, bis(2-ethylhexyl)imidazolium acetate, 1-(2-ethylhexyl)-3-dodecylimidazolium acetate, 1,3-didodecylimidazolium acetate, 1,3-dimethylimidazolium 2-ethylhexanoate, 1-butyl-3-methylimidazolium 2-ethylhexanoate, 1-methyl-3-octylimidazolium 2-ethylhexanoate, 1-methyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-methyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate xanthates, 1-dodecyl-3-methylimidazolium 2-ethylhexanoate, 1,3-dibutylimidazolium 2-ethylhexanoate, 1-butyl-3-octylimidazolium 2-ethylhexanoate, 1-butyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-butyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-butyl-3-dodecylimidazolium 2-ethylhexanoate, 1,3-dioctylimidazolium 2-ethylhexanoate, 1-octyl-3-(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1-octyl-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-octylimidazolium 2-ethylhexanoate, 1-(1,1,3,3-tetramethylbutyl)-3-(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-dodecyl-3-(1,1,3,3-tetramethylbutyl) Imidazolium 2-ethylhexanoate, bis(2-ethylhexyl)imidazolium 2-ethylhexanoate, 1-(2-ethylhexyl)-3-dodecylimidazolium 2-ethylhexanoate, 1,3-didodecylimidazolium 2-ethylhexanoate are preferred, and bis(2-ethylhexyl)imidazolium acetate and bis(2-ethylhexyl)imidazolium 2-ethylhexanoate are more preferred.

[0036] The imidazolium carboxylate (1) may be a commercially available product. The imidazolium carboxylate (1) may be obtained by a known method, or may be produced by the method described below.

[0037] The imidazolium carboxylate of formula (1) is obtained by reacting a dicarbonyl compound represented by formula (4) below, a primary amine compound represented by formula (5a) and formula (5b) below, formaldehyde, and a carboxylic acid represented by formula (6) below.

[0038] Formula (4):

[0039] [ka] (In the formula, R 2 and R 3 is as defined above.)

[0040] Formula (5a):

[0041] R 1 -NH2(5a) (In the formula, R 1is as defined above.)

[0042] Formula (5b):

[0043] R 4 -NH2(5b) (In the formula, R 4 is as defined above.)

[0044] Formula (6):

[0045] [ka] (In the formula, R 5 is as defined above.)

[0046] The dicarbonyl compound represented by formula (4) (hereinafter referred to as dicarbonyl compound (4)) is preferably glyoxal, diacetyl, 3,4-hexanedione, 2,3-pentanedione, 2,3-heptanedione, 5-methyl-2,3-hexanedione, 3-methyl-2,3-cyclopentanedione, 1,2-cyclohexanedione, 1-phenyl-1,2-propanedione, or dibenzoyl, more preferably glyoxal or diacetyl, more preferably glyoxal.

[0047] The primary amine compound represented by formula (5a) (hereinafter referred to as primary amine compound (5a)) and the primary amine compound represented by formula (5b) (hereinafter referred to as primary amine compound (5b)) include methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, hexylamine, octylamine, 1,1,3,3-tetramethylbutylamine, 2-ethylhexylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, 2-methoxyethylamine, 2-ethoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-prop ... The primary amine compound is at least one selected from the group consisting of aniline, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-(2-ethylhexyloxy)propylamine, allylamine, benzylamine, aniline, 2,6-diisopropylaniline, and 2,4,6-trimethylaniline, and is preferably methylamine, ethylamine, butylamine, hexylamine, octylamine, 1,1,3,3-tetramethylbutylamine, 2-ethylhexylamine, dodecylamine, octadecylamine, or benzylamine, and more preferably methylamine, butylamine, octylamine, or 2-ethylhexylamine.

[0048] The carboxylic acid represented by formula (6) (hereinafter referred to as carboxylic acid (6)) is preferably formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, capric acid, lauric acid, tetradecylic acid, palmitic acid, octadecylic acid, cyclohexanoic acid, ethoxyacetic acid, propoxyacetic acid, 2-(2-methoxyethoxy)acetic acid, 2-(2-ethoxyethoxy)acetic acid, 2-(2-propoxyethoxy)acetic acid, 3-methoxypropanoic acid, 3-ethoxypropanoic acid, 3-(2-methoxyethoxy)propanoic acid, 3-(2- ... Examples of suitable carboxylic acids include 3-(2-propoxyethoxy)propanoic acid, 3-(3-methoxypropoxy)propanoic acid, 3-(3-ethoxypropoxy)propanoic acid, 3-(3-propoxypropoxy)propanoic acid, oleic acid, linoleic acid, sorbic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, salicylic acid, and trifluoroacetic acid. More preferred are formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and 2-ethylhexanoic acid. Particularly preferred are acetic acid and 2-ethylhexanoic acid.

[0049] The dicarbonyl compound (4) may be used as it is in the form of an aqueous solution or an alcohol solution such as methanol or butanol.

[0050] The amount of primary amine compound (5a) and primary amine compound (5b) (hereinafter, primary amine compound (5a) and primary amine compound (5b) are collectively referred to as amine compound (5)) used is typically 0.1 to 10 moles, preferably 0.5 to 3 moles, of amine compound (5) per mole of dicarbonyl compound (4). Two moles of amine compound (5) react with 1 mole of dicarbonyl compound (4) to produce 1 mole of imidazolium carboxylate (1). However, if the amount of amine compound (5) is less than 2 moles, a polymer of dicarbonyl compound (4) (raw material) and dicarbonyl compound (4) will be present in addition to the desired imidazolium carboxylate (1). Furthermore, if more than 2 moles of amine compound (5) are used per mole of dicarbonyl compound (4), an excess amount of amine compound (5) will be present in addition to the desired imidazolium carboxylate (1). Amidate compound (3) can also be obtained by using imidazolium carboxylate (1) in the presence of a compound other than these imidazolium carboxylates (1).

[0051] The ratio of the primary amine compound (5a) to the primary amine compound (5b) is not particularly limited, and is in the range of primary amine compound (5a):primary amine compound (5b)=0:100 to 100:0 (molar ratio). When the primary amine compound (5a):primary amine compound (5b)=0:100 or primary amine compound (5a):primary amine compound (5b)=100:0, R 1 =R 4 Also, R 1 =R 4 In other cases, that is, when the ratio of the primary amine compound (5a):primary amine compound (5b) is not 0:100 or 100:0, the compound of formula (1) can be a mixture of compounds represented by the following formulas (1-1), (1-2), and (1-3).

[0052] [ka]

[0053] (In formula (1-1), formula (1-2), and formula (1-3), R1 , R 2 , R 3 , R 4 , R 5 are each as defined above.) The ratio of the compound represented by formula (1-1), the compound represented by formula (1-2), and the compound represented by formula (1-3) in this mixture varies depending on the ratio of the primary amine compound (5a) and the primary amine compound (5b) used in the reaction. The compound represented by formula (1-1), the compound represented by formula (1-2), and the compound represented by formula (1-3) are all included in the imidazolium carboxylate (1).

[0054] Formaldehyde may be used as it is in the form of an aqueous solution or an alcohol solution such as methanol or butanol. The amount of formaldehyde used is usually 0.1 to 10 mol, preferably 0.5 to 5.0 mol, per 1 mol of the dicarbonyl compound (6).

[0055] The amount of the carboxylic acid (6) used is usually 0.1 to 10 moles, preferably 0.5 to 2 moles, and more preferably 1 to 1.5 moles, per mole of the dicarbonyl compound (4).

[0056] The optimum reaction temperature varies depending on the starting materials, solvent, etc. used, but is usually −10° C. or higher, preferably 0° C. to 100° C. The reaction time is not particularly limited, but is preferably 0.5 to 48 hours.

[0057] A solvent may or may not be used. When a solvent is used, the solvent to be used is not particularly limited as long as it does not affect the reaction. Specific examples of solvents include aromatic hydrocarbons such as toluene, benzene, and xylene; aliphatic or alicyclic hydrocarbons such as methylcyclohexane, cyclohexane, hexane, heptane, and octane; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane; ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; lower alcohols such as methanol and ethanol; N,N-dimethylformamide, acetonitrile, and water. Preferred are aromatic hydrocarbons, lower alcohols, and water, with toluene and water being particularly preferred. Two or more solvents can also be used in combination as needed.

[0058] The amount of the solvent used is usually 50 parts by mass or less, preferably 0.1 to 10 parts by mass, per part by mass of the dicarbonyl compound (4).

[0059] If necessary, the reaction may be carried out in an inert gas atmosphere such as nitrogen, argon, or helium, which does not affect the reaction.

[0060] After the reaction is complete, the imidazolium carboxylate (1) can be isolated by removing impurities (e.g., unreacted raw materials) by washing with an organic solvent or by concentrating the reaction mixture, and if necessary, purification such as recrystallization may be carried out.

[0061] During the production of imidazolium carboxylate (1), carboxylic acid (6) may be used in excess of the stoichiometric amount, and may remain in imidazolium carboxylate (1). In this case, the remaining carboxylic acid (6) can be converted to the corresponding ester compound by reacting it with a carbonate ester.

[0062] Specific examples of carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, and dihexyl carbonate, and cyclic alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate, of which dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate are preferred, and dimethyl carbonate is particularly preferred.

[0063] The amount of carbonate ester used is typically 1 mole or more, preferably 1 to 6 moles, per mole of the remaining carboxylic acid (6). When imidazolium carboxylate (1) contains water in addition to carboxylic acid (6), the water reacts with the carbonate ester. Therefore, it is preferable to use an excess of carbonate ester, typically 1 mole or more, preferably 1 to 6 moles, per mole of the total of carboxylic acid (6) and water contained in imidazolium carboxylate (1). The carboxylic acid (6) can be converted to the corresponding ester compound at a reaction temperature of 30 to 100°C for a reaction time of 1 to 8 hours. The converted ester compound can be removed by washing with an organic solvent or concentrating the reaction solution, thereby removing the carboxylic acid (6) contained in imidazolium carboxylate (1). Even when imidazolium carboxylate (1) containing an ester compound converted by a carbonate ester is used, the target amidate compound (3) can be obtained by the production method of the present invention.

[0064] Next, the polyisocyanate compound (2) will be described.

[0065] In formula (2), A represents any one of the following residues (i) to (v) (hereinafter sometimes simply referred to as "residue"). (i) a residue obtained by removing an isocyanate group from an aliphatic polyisocyanate; (ii) a residue obtained by removing an isocyanate group from an alicyclic polyisocyanate; (iii) a residue obtained by removing an isocyanate group from an aromatic polyisocyanate; (iv) a residue obtained by removing an isocyanate group from an araliphatic polyisocyanate; (v) A residue obtained by removing an isocyanate group from a modified isocyanate formed from at least one member selected from the group consisting of an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an araliphatic polyisocyanate.

[0066] Aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, or modified isocyanates thereof are compounds having an isocyanate group, and the residue A itself represents the portion of the aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, or modified isocyanates thereof other than the isocyanate group. The residue A is typically an x-valent hydrocarbon group that may have a substituent other than an isocyanate group, and preferably comprises an x-valent hydrocarbon group that may be substituted with a heteroatom or a halogen atom. In this case, the hydrocarbon group preferably has 1 to 100 carbon atoms. In another embodiment, the residue preferably does not have an active hydrogen group such as a hydroxyl group or an amino group. Note that the x in the x-valent is the same as the x in formula (2).

[0067] Examples of the substituent of the x-valent hydrocarbon group represented by residue A, which may have a substituent other than an isocyanate group, include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a dialkylamino group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, a sulfonyl group, a (monoalkylamino)carbonylamino group, or a (dialkylamino)carbonylamino group. The hydrocarbon group of residue A may be substituted with a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. When the hydrocarbon group of residue A is substituted with a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has a group such as -O-, -N<, -S-, or -SO2-, and the hydrocarbon chain is interrupted by these groups.

[0068] Examples of the substituted or unsubstituted x-valent hydrocarbon group include alkylene groups such as ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decylene, n-dodecylene, n-octadecylene, cyclohexylene, cyclohexane-1,2-diylbismethylene, and cyclohexane-1,4-diylbismethylene; p-phenylene, m-phenylene, and 2-methyl-m-phenylene. Examples of the alkylene group include arylene groups such as m-phenylene group, 4-methyl-m-phenylene group, 5-methyl-m-phenylene group, and naphthylene group; aryl alkylene groups such as phenylethylene group, 1-phenylpropylene group, 2-phenylpropylene group, 1-phenylbutylene group, 2-phenylbutylene group, and naphthylethylene group; and alkylene arylene groups such as methylene diphenylene group and polymethylene polyphenylene group, which are formed by appropriately combining the above-mentioned alkylene group and arylene group.

[0069] Preferred examples of the residue A include the following groups:

[0070] [ka]

[0071] (In the formula, m is an integer of 0 to 4.)

[0072] x is an integer of 2 or more and 20 or less, preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3.

[0073] The polyisocyanate compound (2) may be an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, an araliphatic polyisocyanate, or a modified isocyanate thereof. The polyisocyanate compound (2) may be a monomer, a dimer, a trimer, or a polymer.

[0074] Examples of the aliphatic polyisocyanate include aliphatic diisocyanates, lysine triisocyanate, 4-isocyanatomethyl-1,8-octamethylene diisocyanate, and bis(2-isocyanatoethyl) 2-isocyanatoglutarate.

[0075] The aliphatic diisocyanate is preferably one having 4 to 30 carbon atoms, such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter referred to as HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, etc., with HDI being preferred. The aliphatic polyisocyanates may be used alone or in combination of two or more.

[0076] The alicyclic polyisocyanate preferably has 8 to 30 carbon atoms, and specific examples thereof include 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane isocyanurate (hereinafter referred to as IPDI), bis(4-isocyanatocyclohexyl)methane, norbornane diisocyanate, and dimer acid diisocyanate, with IPDI being preferred. The alicyclic polyisocyanates may be used alone or in combination of two or more.

[0077] Examples of aromatic polyisocyanates include aromatic diisocyanates and polymethylene polyphenyl polyisocyanates (hereinafter referred to as polymeric MDI). Examples of aromatic diisocyanates include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylene diisocyanate. Aromatic polyisocyanates may be used alone or in combination of two or more. Preferred are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymeric MDI because of their industrial availability.

[0078] Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, etc. The araliphatic polyisocyanates may be used alone or in combination of two or more.

[0079] Of these polyisocyanate compounds, aromatic polyisocyanates are preferred, and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymeric MDI are more preferred.

[0080] Examples of modified isocyanates include dimer to 20-mer oligomers of the above polyisocyanates produced by forming biuret bonds, urea bonds, isocyanurate bonds, uretdione bonds, urethane bonds, allophanate bonds, oxadiazinetrione bonds, etc. Polyisocyanates having biuret bonds can be obtained by reacting a polyisocyanate with a so-called biuretizing agent such as water, tert-butanol, or urea in a molar ratio of biuretizing agent to isocyanate groups in the polyisocyanate of about 1 / 2 to about 1 / 100, followed by removal of unreacted polyisocyanate and purification. Polyisocyanates having isocyanurate bonds can be obtained, for example, by performing a cyclotrimerization reaction using a catalyst or the like, terminating the reaction when the conversion rate reaches about 5 to about 80% by mass, and then removing unreacted polyisocyanate and purification.

[0081] Polyisocyanate compounds having urethane bonds, which are included in modified isocyanates, can be obtained by reacting a dihydric to hexahydric alcohol compound such as trimethylolpropane with a polyisocyanate in a molar ratio of hydroxyl groups of the alcohol compound to isocyanate groups of the polyisocyanate of about 1 / 2 to about 1 / 100, followed by removal of unreacted polyisocyanate through purification. Purification by removal of unreacted polyisocyanate is not always necessary. The modified isocyanate compound is preferably a dimer or trimer polyisocyanate formed from one or more members selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or polymethylene polyphenyl polyisocyanate.

[0082] Formula (3)

[0083] [ka]

[0084] In formula (3), y and z are integers of 1 or more and 19 or less, and the sum of y and z is 2 or more and 20 or less. Preferably, y and z are 1 to 5 and the sum of y and z is 2 to 6, more preferably, y and z are 1 to 3 and the sum of y and z is 2 to 4, and particularly preferably, y and z are 1 or 2 and the sum of y and z is 2 or 3.

[0085] A, R 1 , R 2 , R 3 , R 4 , R 5 are each as defined above.

[0086] When amidate compound (3) has isomers such as optical isomers, stereoisomers, or positional isomers, a mixture of all isomers is also encompassed by amidate compound (3) unless otherwise specified. For example, when amidate compound (3) has optical isomers, the optical isomers resolved from the racemate can also be encompassed by amidate compound (3). These isomers can be obtained as single compounds by conventional separation techniques (e.g., concentration, solvent extraction, column chromatography, recrystallization, etc.).

[0087] Examples of the amidate compound (3) of the present invention include the following: In the following specific examples, Et represents an ethyl group, Bu represents an n-butyl group, Hept represents an n-heptyl group, Oct represents an n-octyl group, 1-EtPent represents a 1-ethylpentyl group, and 2-EtHex represents a 2-ethylhexyl group.

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] In the formulas (3-5-1) to (3-5-18), m is an integer of 0 to 4.

[0092] [ka]

[0093] In the formulas (3-6-1) to (3-6-18) and (3-7-1) to (3-7-18), m is an integer of 0 to 4.

[0094] [ka]

[0095] In the formulas (3-8-1) to (3-8-18), m is an integer of 0 to 4.

[0096] The amidate compound (3) is preferably a compound represented by the formula (3-1-4), (3-1-6), (3-1-10), (3-1-12), (3-1-16), (3-1-18), (3-2-4), (3-2-6), (3-2-10), (3-2-12), (3-2-16), (3-2-18), (3-3-4), (3-3-6), (3-3-10), ( 3-3-12), (3-3-16), (3-3-18), (3-4-4), (3-4-6), (3-4-10), (3-4-12), (3-4-16), (3-4-18), (3-5-4), (3-5-6), (3-5-10), (3-5-12), (3-5-16), (3-5-18), (3-6-4), (3-6-6), (3-6- 10), (3-6-12), (3-6-16), (3-6-18), (3-7-4), (3-7-6), (3-7-10), (3-7-12), (3-7-16), (3-7-18), (3-8-4), (3-8-6), (3-8-10), (3-8-12), (3-8-16), and (3-8-18), are more preferred. or compounds represented by formula (3-1-6), (3-1-18), (3-2-6), (3-2-18), (3-3-6), (3-3-18), (3-4-6), (3-4-18), (3-5-6), (3-5-18), (3-6-6), (3-6-18), (3-7-6), (3-7-18), (3-8-6), and (3-8-18).

[0097] In the production method of the present invention, in addition to the target amidate compound (3), by-products represented by formula (P), formula (Q), and formula (R) may be present in the reaction mixture.

[0098] [ka]

[0099] (In the formula, R 1 ~R 5 , x, y, z, and A are as defined above. The by-products represented by formulae (P), (Q), and (R) may be separated, and the amidate compound (3) isolated and used as a blocking agent unblocking catalyst for blocked isocyanates. Alternatively, a mixture containing at least one by-product represented by formulae (P), (Q), and (R) together with the amidate compound (3) can be used as a blocking agent unblocking catalyst for blocked isocyanates. Alternatively, a mixture containing at least one by-product represented by formulae (P), (Q), and (R) together with the amidate compound (3) can be mixed with a blocked isocyanate and a compound having an isocyanate-reactive group to form a thermosetting resin composition. Among the by-products represented by formulae (P), (Q), and (R), the by-product represented by formula (R) contains an amidate group, just like the amidate compound (3), and is therefore believed to function as a blocking agent unblocking catalyst for blocked isocyanates, just like the amidate compound (3).

[0100] A mixture containing amidate compound (3) and at least one by-product represented by formula (P), formula (Q), or formula (R) is encompassed by the amidate compound (3) of the present invention.

[0101] <Blocking agent dissociation catalyst for blocked isocyanates> The amidate compound (3) can be used as a blocking agent dissociation catalyst for blocked isocyanates (hereinafter referred to as a blocking agent dissociation catalyst). A blocking agent dissociation catalyst is a catalyst that dissociates the blocking agent that blocks the isocyanate groups of blocked isocyanates and inhibits their reaction, and can promote the reaction between the regenerated isocyanate groups and coexisting isocyanate-reactive groups.

[0102] When the amidate compound (3) is used as a blocking agent unblocking catalyst for blocked isocyanates, R 1 and R 4are the same or different and represent hydrocarbon groups having 1 to 20 carbon atoms which may be substituted with a heteroatom, preferably hydrocarbon groups having 1 to 12 carbon atoms which may be substituted with a heteroatom, and particularly preferably hydrocarbon groups having 1 to 8 carbon atoms which may be substituted with a heteroatom. The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 1,1,3,3-tetramethylbutyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an allyl group, a benzyl group, a cyclohexyl group, an adamantyl group, a phenyl group, a 2,6-diisopropylphenyl group, a 2,4,6-trimethylphenyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, and a 2-(dimethylamino)ethyl group. Preferred are methyl, ethyl, propyl, isopropyl, butyl, octyl, dodecyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, benzyl, phenyl, and 2,4,6-trimethylphenyl groups, and particularly preferred are methyl, ethyl, butyl, octyl, 2-ethylhexyl, and benzyl groups.

[0103] R 1 and R 4 In the formula (I), examples of heteroatoms include nitrogen, oxygen, and sulfur atoms. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, the hydrocarbon group has a group such as -O-, -N<, -S-, or -SO2-, and the hydrocarbon chain is interrupted by this group. When a hydrocarbon group is substituted with a heteroatom such as an oxygen atom, nitrogen, or sulfur atom, it is preferred that the hydrocarbon group is substituted with an oxygen atom and the hydrocarbon chain is interrupted by an -O- group.

[0104] The blocker dissociation catalyst containing the amidate compound (3) will now be described.

[0105] The blocking agent dissociation catalyst may be used alone or in combination with two or more other catalysts, and may also be used in combination with a solvent, etc., if necessary.

[0106] The solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, etc.; alcohol solvents such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; polyol solvents such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc.; and water. These solvents may be used alone or in combination of two or more.

[0107] The blocking agent dissociation catalyst of the present invention is a catalyst that promotes the curing of a mixture of a blocked isocyanate and a compound having an isocyanate-reactive group.

[0108] The object of the present invention can be fully achieved as long as the blocking agent dissociation catalyst of the present invention contains the amidate compound (3) as an active ingredient, and may contain a known blocking agent dissociation catalyst as needed.

[0109] The blocking agent dissociation catalyst of the present invention can be suitably used, for example, as a catalyst for a method for dissociating a blocking agent from a blocked isocyanate, in which the blocked isocyanate is heated in the presence of the blocking agent dissociation catalyst.

[0110] In the method for dissociating a blocking agent of the present invention, the amount of the blocking agent dissociating catalyst used is not particularly limited, and the amount of the amidate compound (3) contained in the blocking agent dissociating catalyst is usually 0.01 to 15% by weight, preferably 0.05 to 10% by weight, and more preferably 0.1 to 5% by weight, based on the solid content of the thermosetting resin composition described below.

[0111] In this specification, the term "solid content" refers to the total mass of components in a thermosetting resin composition excluding the solvent described below. Therefore, when a resin composition does not contain a solvent, the total mass of the composition is equal to the solid content.

[0112] The reaction temperature varies depending on the blocked isocyanate used, but can be about 60 to 250° C., preferably about 80 to 200° C. The reaction time is about 30 seconds to 5 hours, preferably about 30 seconds to 2 hours.

[0113] <Thermosetting resin composition> The thermosetting resin composition of the present invention contains an amidate compound (3), a blocked isocyanate, and a compound having an isocyanate-reactive group.

[0114] Examples of blocked isocyanates include compounds obtained by reacting a known polyisocyanate with a known blocking agent to block the isocyanate groups in the polyisocyanate with the blocking agent. The blocked isocyanate may be used alone or in combination of two or more types.

[0115] In the present invention, the polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups, and known polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, modified isocyanates thereof, etc. These polyisocyanates may be used alone or in combination of two or more.

[0116] Examples of the aliphatic polyisocyanate include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.

[0117] Examples of alicyclic polyisocyanates include 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane isocyanurate (isophorone diisocyanate), bis(4-isocyanatocyclohexyl)methane, norbornane diisocyanate, and dimer acid diisocyanate.

[0118] Examples of aromatic polyisocyanates include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylene diisocyanate.

[0119] Examples of the aromatic aliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, and the like.

[0120] Examples of modified isocyanates include isocyanate group-terminated compounds obtained by reacting the above-mentioned polyisocyanate compounds with compounds having an active hydrogen group, and polyisocyanate compounds and / or reaction products of the isocyanate group-terminated compounds (for example, adduct-type polyisocyanates, and isocyanate-modified products obtained by allophanation reaction, carbodiimidation reaction, uretdione reaction, isocyanurate reaction, uretonimine reaction, biuret reaction, etc.).

[0121] Examples of known blocking agents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, 2-ethylhexanol, and butyl cellosolve; fluorinated alcohols such as 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoro-2-propanol; phenols such as phenol, cresol, and 2-hydroxypyridine; amines such as diisopropylamine; ε-caprolactam, δ-valerolactam, γ-butanol; Examples of the oxime include lactams such as thiolactam, oximes such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, and methyl isobutyl ketoxime, ketoenols such as acetylacetone, pyrazoles such as 1,2-pyrazole and 3,5-dimethylpyrazole, and triazoles such as triazole. Preferred are lactams, oximes, and pyrazoles, and particularly preferred are ε-caprolactam, methyl ethyl ketoxime, and 3,5-dimethylpyrazole.

[0122] Examples of compounds having an isocyanate-reactive group include compounds having two or more active hydrogen groups, such as polyols, polyamines, alkanolamines, etc. These compounds having an isocyanate-reactive group may be a mixture of two or more types.

[0123] In the present invention, a polyol is a compound having two or more hydroxyl groups. Examples of polyols include polyether polyols, polyester polyols, acrylic polyols, polyolefin polyols, fluorine polyols, polycarbonate polyols, and polyurethane polyols. These polyols may be a mixture of two or more types.

[0124] Examples of polyether polyols include active hydrogen compounds such as aliphatic amine polyols, aromatic amine polyols, Mannich polyols, polyhydric alcohols, polyhydric phenols, and bisphenols, as well as compounds obtained by adding alkylene oxides to these compounds. These polyether polyols may be a mixture of two or more types.

[0125] Examples of aliphatic amine polyols include alkylenediamine polyols and alkanolamine polyols. These polyol compounds are polyfunctional polyol compounds with terminal hydroxyl groups, which are obtained by ring-opening addition of at least one cyclic ether, such as ethylene oxide or propylene oxide, to alkylenediamine or alkanolamine as an initiator. Any known alkylenediamine can be used without limitation. Specifically, alkylenediamines having 2 to 8 carbon atoms, such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine, are suitable. These aliphatic amine polyols may be a mixture of two or more.

[0126] Aromatic amine polyols are polyfunctional polyether polyol compounds with terminal hydroxyl groups, which are prepared by ring-opening addition of 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 the initiator. Specific examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, and naphthalenediamine. Among these, 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.

[0127] Mannich polyols are active hydrogen compounds obtained by the Mannich reaction of phenol and / or its alkyl-substituted derivatives, formaldehyde, and alkanolamine, or polyol compounds obtained by ring-opening addition polymerization of the active hydrogen compounds with at least one of ethylene oxide and propylene oxide. These Mannich polyols may be a mixture of two or more types.

[0128] 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 be a mixture of two or more kinds.

[0129] Examples of polyhydric phenols include pyrogallol, hydroquinone, etc. These polyhydric phenols may be a mixture of two or more kinds.

[0130] Examples of bisphenols include bisphenol A, bisphenol S, bisphenol F, low condensates of phenol and formaldehyde, etc. These bisphenols may be a mixture of two or more kinds.

[0131] Examples of polyester polyols include polyester polyols obtained by a condensation reaction of a dibasic acid selected from the group consisting of carboxylic acids such as succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, and terephthalic acid, either alone or in combination, with a polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, and glycerin, and polycaprolactones obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol. These polyester polyols may also be a mixture of two or more types.

[0132] Acrylic polyols are compounds obtained by copolymerizing a single or mixture of ethylenically unsaturated bond-containing monomers having a hydroxyl group with a single or mixture of other ethylenically unsaturated bond-containing monomers copolymerizable therewith. Examples of ethylenically unsaturated bond-containing monomers having a hydroxyl group include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate, with hydroxyethyl acrylate and hydroxyethyl methacrylate being preferred. These acrylic polyols may also be mixtures of two or more types.

[0133] Examples of other ethylenically unsaturated bond-containing monomers copolymerizable with the ethylenically unsaturated bond-containing monomer having a hydroxyl group include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, and phenyl acrylate, as well as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate. methacrylic acid esters such as lauryl methacrylate, benzyl methacrylate, and phenyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; unsaturated amides such as acrylamide, methacrylamide, N,N-methylenebisacrylamide, diacetone acrylamide, diacetone methacrylamide, maleic acid amide, and maleimide; vinyl monomers such as glycidyl methacrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate; and vinyl monomers having a hydrolyzable silyl group such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane.

[0134] Examples of polyolefin polyols include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, etc. These polyolefin polyols may be a mixture of two or more kinds.

[0135] Fluorine polyols are polyols containing fluorine in the molecule, and examples thereof include copolymers of fluoroolefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, monocarboxylic acid vinyl esters, etc. These fluorine polyols may be mixtures of two or more kinds.

[0136] Examples of polycarbonate polyols include those obtained by condensation polymerization of low-molecular-weight carbonate compounds, such as dialkyl carbonates (e.g., dimethyl carbonate), alkylene carbonates (e.g., ethylene carbonate), and diaryl carbonates (e.g., diphenyl carbonate), with the low-molecular-weight polyols used in the polyester polyols described above. These polycarbonate polyols may be a mixture of two or more types.

[0137] Polyurethane polyols can be obtained by a conventional method, for example, by reacting a polyol with a polyisocyanate. Examples of polyols that do not contain a carboxyl group include low-molecular-weight ones such as ethylene glycol and propylene glycol, and high-molecular-weight ones such as acrylic polyols, polyester polyols, and polyether polyols. These polyurethane polyols may be a mixture of two or more types.

[0138] In the present invention, polyamine is a compound having two or more primary or secondary amino groups. Examples of polyamine include low-molecular-weight polyamines, high-molecular-weight polyamines, and alkanolamines. These polyamines may be a mixture of two or more types.

[0139] Examples of low-molecular-weight polyamines include aromatic amines such as 4,4'-diphenylmethanediamine, aromatic aliphatic amines such as 1,3- or 1,4-xylylenediamine or mixtures thereof, alicyclic amines such as 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, and 1,4-cyclohexanediamine, and aliphatic amines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, hydrazine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. These low-molecular-weight polyamines may be a mixture of two or more kinds.

[0140] Examples of high molecular weight polyamines include polyoxyalkylene diamines (weight average molecular weight 400 to 4000) and polyoxyalkylene triamines (weight average molecular weight 400 to 5000). These high molecular weight polyamines may be a mixture of two or more kinds.

[0141] Examples of alkanolamines include monoethanolamine, diethanolamine, N-(2-aminoethyl)ethanolamine, N-(2-hydroxypropyl)ethylenediamine, monopropanolamine, monoisopropanolamine, dipropanolamine, diisopropanolamine, ethylene glycol bis(3-aminopropyl)ether, neopentanolamine, and methylethanolamine.

[0142] In the thermosetting resin composition of the present invention, the blending ratio of the blocked isocyanate to the compound having an isocyanate-reactive group is determined depending on the required physical properties and is not particularly limited, but is usually in the range of [available isocyanate groups (mol) of blocked isocyanate] / [active hydrogen groups (mol) of compound having an isocyanate-reactive group] = 0.2 to 3. The available isocyanate groups of the blocked isocyanate refer to the isocyanate groups that are regenerated when the blocking agent dissociates from the blocked isocyanate.

[0143] In the thermosetting resin composition of the present invention, the amount of the blocking agent unbinding catalyst of the present invention used is not particularly limited, and is usually an amount such that the amount of the amidate compound (3) contained in the blocking agent unbinding catalyst in the thermosetting resin composition is 0.01 to 15% by weight, preferably 0.05 to 10% by weight, and more preferably 0.1 to 5% by weight, based on the solid content of the thermosetting resin composition.

[0144] In the thermosetting resin composition of the present invention, known catalysts, additives, pigments, solvents, etc. commonly used in the art for producing polyurethanes can be used as needed.

[0145] Known catalysts for producing polyurethanes are not particularly limited, and examples thereof include tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octylate, and tin laurate; bismuth compounds such as bismuth octylate, bismuth naphthenate, and bismuth acetylacetonate; tetra-n-butyl titanate; and 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 ( tertiary amine compounds such as 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 salts; and quaternary ammonium salt compounds such as tetraalkylammonium organic acid salts such as tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

[0146] The additives are not particularly limited, and examples thereof include hindered amine-based, benzotriazole-based, benzophenone-based, and other ultraviolet absorbers; perchlorate-based, hydroxylamine-based, and other coloration inhibitors; hindered phenol-based, phosphorus-based, sulfur-based, hydrazide-based, and other antioxidants; tin-based, zinc-based, amine-based, and other urethane catalysts; and other leveling agents, rheology control agents, pigment dispersants, and the like.

[0147] The pigment is not particularly limited, and examples thereof include organic pigments such as quinacridone, azo, and phthalocyanine pigments, inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica, as well as other pigments such as carbon pigments, metal foil pigments, and anti-rust pigments.

[0148] The solvent is not particularly limited, and examples thereof include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, butyl acetate, cellosolve acetate, etc.; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.; polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, glycerin, etc.; water, etc.; and these solvents may be used alone or in combination of two or more.

[0149] When storage at high temperatures is anticipated, the thermosetting resin composition of the present invention can be prepared as a two-part thermosetting composition by separating the blocked isocyanate and the compound having an isocyanate-reactive group, and the two-part thermosetting compositions can be mixed together at the time of use to obtain the thermosetting resin composition of the present invention. In such a case, the blocking agent unblocking catalyst can be added when mixing the two-part thermosetting composition, or the compound having an isocyanate-reactive group and the blocking agent unblocking catalyst can be mixed in advance.

[0150] The thermosetting resin composition of the present invention can be used for paints for automobiles, buildings, metal products such as steel furniture, wood products such as musical instruments, mechanical vehicles such as construction machinery, building materials such as sashes, electrical home appliances such as office machines, coating materials for artificial leather and rubber rolls, inks, adhesives, pressure-sensitive adhesives, sealing materials for electronic components, sealing materials for automobiles and buildings, molding materials for 3D printers, etc.

[0151] Next, a method for curing the thermosetting resin composition of the present invention will be described.

[0152] In the method of the present invention, a mixture of a blocked isocyanate and a compound having an isocyanate-reactive group is heated in the presence of the above-mentioned blocking agent dissociation catalyst.

[0153] The reaction temperature varies depending on the blocked isocyanate used, but can be about 60 to 250° C., preferably about 80 to 200° C. The reaction time can be about 30 seconds to 5 hours, preferably about 1 minute to 60 minutes.

[0154] The cured product of the present invention can be produced by the above-described method for curing the thermosetting resin composition of the present invention. [Example]

[0155] The present invention will be explained in more detail using Production Examples and Examples, but the present invention is not limited to these Examples.

[0156] (I) 1 H-NMR analysis conditions Equipment: Bruker AV400 Frequency: 400MHz

[0157] (II) Liquid chromatography mass spectrometry (hereinafter referred to as LC-MS) conditions LC device: Thermo Fisher Scientific UltiMate 3000 Column: SUMIPAX ODS Z-CLUE (length 50 mm, inner diameter 3.0 mm, particle size 2 μm) manufactured by Sumika Chemical Analysis Center, Ltd. Column temperature: 35℃ Detection method: Photodiode array (PDA) detector, 240 nm Flow rate: 0.5mL / min Mobile phase: A = 10 mM ammonium formate aqueous solution, B = methanol Gradient: See Table 1 below Sample: 10 mg sample / 20 mL methanol Sample injection volume: 1 μL MS device: EXACTIVE Ionization: ESI+ Scan range: m / z 50-1000

[0158] [Table 1]

[0159] (III) Curing temperature measurement conditions Equipment: Cyber ​​Corporation's Madoka automatic curing time measuring device Stirring rod: Model number 3JC-5060W Stirring speed: rotation 100 rpm, revolution 25 rpm

[0160] (IV) Method for measuring NCO group content (%) of polymeric MDI The NCO group content (%) herein refers to the amount of isocyanate groups present in the polyisocyanate expressed as a mass fraction, and is measured and calculated by the following method.

[0161] 1.6341 g of polymeric MDI (Sumidur 44V20, manufactured by Sumika Covestro Urethane Co., Ltd.) was placed in a 200 mL Erlenmeyer flask and 50 mL of a 0.2 mol / L dibutylamine toluene solution was added to dissolve the polymeric MDI. Next, a small amount of bromocresol green was added to the polymeric MDI solution, and a 0.5 mol / L hydrochloric acid ethanol solution was added dropwise using a burette. A similar test was also conducted using the same procedure, except that no polymeric MDI was used. The amount of hydrochloric acid ethanol solution required for the solution in the flask to change color from blue to yellow was 50.17 mL in the test using the polymeric MDI, and 25.24 mL in the test using the polymeric MDI.

[0162] Using the following formula, the NCO group content of the polymeric MDI was calculated to be 32.0%. NCO group content (%) = [{(Test hydrochloric acid ethanol solution titration volume (mL) - Sample hydrochloric acid ethanol solution titration volume (mL)} x hydrochloric acid ethanol solution concentration (mol / mL)] / polymeric MDI weight (g) x 4.202 = [{(50.17 (mL) - 25.24 (mL)} x 0.5 (mol / mL)] / 1.6341 (g) x 4.202

[0163] (V) Calculation method for effective NCO group content (%) The effective NCO group content (%) here quantifies the amount of blocked isocyanate groups present in the blocked isocyanate after the blocking reaction and capable of participating in a crosslinking reaction, and is expressed as the mass (%) of the isocyanate groups and calculated by the following formula: Effective NCO group content (%) = {(solid content of blocked isocyanate (mass (%))) x (mass of polyisocyanate used in the reaction x NCO group content (%) of precursor polyisocyanate)} / (resin mass of blocked isocyanate after blocking reaction). If the blocked isocyanate has been diluted with a solvent, etc., the value in the diluted state should be recorded.

[0164] (VI) Calculation method for solids content Approximately 1.5 g of the sample was heated at 110°C for 3 hours, and the solid content (%) in the sample was calculated from the mass before and after heating.

[0165] (VII) Composition of the thermosetting resin composition Blocked isocyanate, polyol, and amidate compound were added so that the ratio of available NCO groups (mol):hydroxyl groups (mol):amidate groups (mol) was 1.00:0.95:0.05, and methyl isobutyl ketone was added so that the total amount of solvent was 1.0 times the weight of the solid content of the blocked isocyanate. The available NCO groups (mol) and hydroxyl groups (mol) were calculated using the following formula. Available NCO groups (mol) = Amount of blocked isocyanate charged (g) ÷ Available NCO group content of blocked isocyanate (%) ÷ 4.202 Hydroxyl groups (mol) = Polyol charge (g) × Polyol hydroxyl value (mgKOH / g) ÷ 56.1

[0166] Amidate group In this specification, the skeleton represented by the following formula (A) is referred to as an amidate group.

[0167] [ka]

[0168] (In the formula, R 1 ~R 4 are each as defined above.)

[0169] In the examples, the amidate group concentration was calculated by the following method: An internal standard substance (Pmmol) such as tetralin or dimethyl sulfone is added to the amidate compound (Qg), which is then dissolved in a deuterated solvent. 1 H-NMR analysis was performed. 1 and R 4 The integrated intensity (S) of the peak corresponding to R hydrogen atoms bonded to the carbon atom adjacent to the nitrogen atom of the imidazolium skeleton and the integrated intensity (U) of the peak corresponding to T hydrogen atoms bonded to any group of the internal standard substance were determined, and the amidate group concentration (mmol / g) was calculated using the following formula: P x S x T / (R x U x Q). In the examples, wt% indicates mass%.

[0170] Production Example 1 Synthesis of [D2EHI][OAc]

[0171] [ka]

[0172] A 500 mL four-neck reactor, purged with nitrogen, was charged with 52.3 g (0.87 mol) of acetic acid, 42.1 g (0.56 mol) of 41 wt% aqueous formalin solution, and 82.8 g (0.58 mol) of 41 wt% aqueous glyoxal solution, and heated to 50°C. Next, 150.1 g (1.16 mol) of 2-ethylhexylamine was added dropwise to the reactor over 2 hours, and the mixture was stirred for an additional 2.5 hours. Subsequently, 3.4 g (0.05 mol) of 41 wt% aqueous formalin solution and 6.7 g (0.05 mol) of 41 wt% aqueous glyoxal solution were added to the reaction solution, and the mixture was stirred for an additional 30 minutes. The resulting reaction solution was concentrated under reduced pressure, yielding 225.8 g of a dark brown viscous liquid. Tetralin was added as an internal standard to the resulting dark brown viscous liquid. 1 H-NMR analysis revealed that the dark brown viscous liquid contained 198.4 g (0.56 mol, 96.9% yield) of [D2EHI][OAc] and 25.2 g (0.42 mol) of acetic acid. 1 The results of H-NMR analysis are shown below. 1 H-NMR(DMSO-d6)δ(ppm)=9.35(s,1H), 7.82(s,2H), 4.15(d,J=7.2Hz,4H), 1.84(m,2H), 1.71(s,3H), 1.25(m,16H), 0.87(t,J=7.2Hz,12H)

[0173] Production Example 2 Synthesis of [D2EHI][2EHA]

[0174] [ka]

[0175] A 200 mL three-neck reactor, purged with nitrogen, was charged with 25.1 g (0.17 mol) of 2-ethylhexanoic acid, 8.6 g (0.12 mol) of 41 wt% aqueous formalin solution, and 16.8 g (0.12 mol) of 41 wt% aqueous glyoxal solution, and heated to 80°C. Next, 30.0 g (0.23 mol) of 2-ethylhexylamine was added dropwise to the reactor over 2 hours at 80°C, followed by stirring for 2 hours. Subsequently, 0.9 g (0.01 mol) of 41 wt% aqueous formalin solution and 1.7 g (0.01 mol) of 41 wt% aqueous glyoxal solution were added to the reaction solution, followed by stirring for an additional 1 hour and 30 minutes. The resulting reaction solution was concentrated under reduced pressure to yield 59.6 g of a dark brown viscous liquid. Tetralin was added as an internal standard to the resulting dark brown viscous liquid. 1 H-NMR analysis revealed that the dark brown viscous liquid contained 35.4 g (0.08 mol, 72.0% yield) of [D2EHI][2EHA] represented by the above formula and 12.1 g (0.08 mol) of 2-ethylhexanoic acid. 1 The results of H-NMR analysis are shown below. 1 H-NMR(CDCl3)δ(ppm)=10.91-10.84(m,1H), 7.07(s,2H), 4.33-4.21(m,4H), 2.23-2.15( m,2H), 1.83-1.77(m,2H), 1.64-1.54(m,4H), 1.48-1.28(m,20H), 0.87(t,J=7.2Hz,12H)

[0176] Production Example 3 Synthesis of [D2EHI][OAc]

[0177] [ka]

[0178] Into a 2 L four-necked reactor purged with nitrogen, 40.0 g (99.5 mmol pure) of [D2EHI][OAc] obtained in Production Example 1 and 39.9 g (443 mmol) of dimethyl carbonate were added and refluxed with stirring for 5 hours. The resulting reaction solution was concentrated under reduced pressure to obtain 34.1 g of a dark brown viscous liquid. Dimethyl sulfone was added as an internal standard substance to the resulting dark brown viscous liquid. 1 H-NMR analysis revealed that the dark brown viscous liquid contained 31.7 g (83.8 mmol, yield 84.2%) of [D2EHI][OAc] represented by the above formula, and that the excess acetic acid had disappeared.

[0179] Production Example 4 Synthesis of [D2EHI][2EHA]

[0180] [ka]

[0181] Into a 100 mL three-necked reactor purged with nitrogen, 16.2 g (22.7 mmol pure) of [D2EHI][2EHA] obtained in Production Example 2 and 16.2 g (180 mmol) of dimethyl carbonate were added and stirred at 90°C for 4 hours. The resulting reaction solution was concentrated under reduced pressure to obtain 12.4 g of a dark brown viscous liquid. Tetralin was added as an internal standard substance to the resulting dark brown viscous liquid. 1 H-NMR analysis revealed that the dark brown viscous liquid contained 9.7 g (22.1 mmol, yield 97.3%) of [D2EHI][2EHA] represented by the above formula, and that excess 2-ethylhexanoic acid had disappeared.

[0182] Production Example 5 Synthesis of MEKO block copolymer of biuret-type HDI A 200 mL three-neck reactor purged with nitrogen was charged with 60.0 g (NCO group: 326 mmol) of biuret HDI (Desmodur N3200A, NCO group content: 22.8%, manufactured by Sumika Covestro Urethane Co., Ltd.) and 36.9 g of methyl isobutyl ketone, and the temperature was raised to 65°C. After the temperature was raised, 0.6 g of triethylamine was added to the reactor. Then, 27.0 g (333 mmol) of methyl ethyl ketoxime and 22.9 g of methyl isobutyl ketone were added dropwise to the reactor and stirred for 2 hours. The resulting reaction solution was concentrated under reduced pressure, and 17.4 g of methyl isobutyl ketone was added to obtain 119.0 g of a MEKO block product of biuret HDI. The solids content of the resulting MEKO block product of biuret HDI was 74.7%, and the effective NCO group content was 11.6%.

[0183] Example 1 Synthesis of D2EHIm_TDI_Me

[0184] [ka]

[0185] A 200 mL three-neck reactor purged with nitrogen was charged with 30.0 g of toluene and heated to reflux. Then, a mixed solution of 30.0 g (79.3 mmol pure) of [D2EHI][OAc] obtained in Production Example 3 and 30.0 g of toluene, and a mixed solution of 15.7 g (89.9 mmol) of tolylene diisocyanate (a mixture of approximately 80% 2,4-tolylene diisocyanate and approximately 20% 2,6-tolylene diisocyanate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 30.0 g of toluene were added dropwise to the reactor over 2 hours and stirred for 2 hours. After stirring, the resulting reaction mixture was concentrated to obtain 38.1 g of a mixture containing the compound represented by the above formula (D2EHIm_TDI_Me) as a dark brown viscous liquid. In addition, 1 The broadening and multiplets of the H-NMR peaks suggested that a reaction product between the modified isocyanate, which was formed by oligomerization of some of the isocyanate groups in the raw material tolylene diisocyanate, and [D2EHI][OAc] was also produced as a by-product. Dimethyl sulfone was added as an internal standard to the resulting dark brown viscous liquid. 1As a result of H-NMR analysis, assuming that the peaks (4.53-4.36 ppm) corresponding to the hydrogen 4H of the methylene group adjacent to the nitrogen atom of the imidazolium group are all derived from D2EHIm_TDI_Me represented by the above formula, it was found that the liquid contained 30.3 g (62.5 mmol, yield 78.7%) of D2EHIm_TDI_Me represented by the above formula, and the amidate group concentration in the dark brown viscous liquid was found to be 1.640 mmol / g. The target product (main product) obtained by ion chromatography 1 The results of H-NMR and mass spectrometry (LC-MS), as well as the results of mass spectrometry (LC-MS) of two by-products, are shown below. (target object, main product)

[0186] [ka]

[0187] 1 H-NMR(CDCl3)δ(ppm)=7.43-6.90(m,5H), 4.53-4.36(m,4H), 2.22-1.91(m,8H), 1.37-1.26(m,16H), 0.88-0.79(m,12H) LC-MS:C 29 H 47 N4O2 + Calculated value = 483.3694, measured value (M + H + )=483.3668 (by-product)

[0188] [ka]

[0189] LC-MS:C 11 H 15 N2O2 + Calculated value = 207.1128, measured value (M+H + )=207.1119

[0190] [ka]

[0191] LC-MS:C 37 H 55 N6O3 + Calculated value = 631.4330, measured value (M + H + )=631.4300 The blocking agent dissociation catalyst of the present invention may be used by isolating only the target product, but even when a mixture containing the target product and by-products is used, the catalyst can sufficiently fulfill its role as a blocking agent dissociation catalyst in a thermosetting resin composition.

[0192] Example 2 Synthesis of D2EHIm_TDI_2EH

[0193] [ka]

[0194] A 100 mL three-neck reactor purged with nitrogen was charged with 10.5 g of toluene and heated to reflux. Subsequently, a mixed solution of 10.0 g (17.8 mmol) of [D2EHI][2EHA] obtained in Production Example 4 and 10.0 g of toluene, and a mixed solution of 3.1 g (17.9 mmol) of tolylene diisocyanate (a mixture of approximately 80% 2,4-tolylene diisocyanate and approximately 20% 2,6-tolylene diisocyanate, manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.1 g of toluene were added dropwise to the reactor over 2 hours and stirred for 1 hour. After stirring, the resulting reaction mixture was concentrated to obtain 9.1 g of a mixture containing the compound represented by the above formula (D2EHIm_TDI_2EH) as a dark brown viscous liquid. Tetralin was added as an internal standard to the resulting dark brown viscous liquid. 1 As a result of H-NMR analysis, assuming that all 4H hydrogen atoms of the methylene group adjacent to the nitrogen atom of the imidazolium group are derived from D2EHIm_TDI_2EH represented by the above formula, it was found that the dark brown viscous liquid contained 5.1 g (9.1 mmol, yield 51.2%) of D2EHIm_TDI_2EH represented by the above formula, and the amidate group concentration in the dark brown viscous liquid was found to be 1.000 mmol / g. The target product (main product) obtained by ion chromatography1 The results of H-NMR and mass spectrometry (LC-MS), as well as the results of mass spectrometry (LC-MS) of two by-products, are shown below. (target object, main product)

[0195] [ka]

[0196] 1 H-NMR(CDCl3)δ(ppm)=7.27-6.86(m, 5H), 4.54-4.47(m,4H), 2.24-2.15(m,3H) , 1.94-1.86(m,1H), 1.78-1.62(m,2H), 1.39-1.19(m,24H), 1.01-0.81(m,18H) LC-MS:C 35 H 59 N4O2 + Calculated value = 567.4633, measured value (M + H + )=567.4598 (by-product)

[0197] [ka]

[0198] LC-MS:C 23 H 39 N2O2 + Calculated value = 375.3006, measured value (M + H + )=375.2982

[0199] [ka]

[0200] LC-MS:C 15 H 25 N2O + Calculated value = 249.1961, measured value (M + H + )=249.1947

[0201] Example 3 Synthesis of D2EHIm_mMDI_Me

[0202] [ka]

[0203] 3.0 g of toluene was placed in a 30 mL three-neck reactor purged with nitrogen and heated to reflux. Then, a mixed solution of 5.0 g (13.2 mmol pure) of [D2EHI][OAc] obtained in Production Example 3 and 5.9 g of toluene, and a mixed solution of 3.7 g (14.8 mmol) of 4,4'-diphenylmethane diisocyanate (Tokyo Chemical Industry Co., Ltd.) and 5.0 g of toluene were added dropwise to the reactor over 2 hours and stirred for 1 hour. After stirring, the resulting reaction mixture was concentrated to obtain 8.3 g of a mixture containing the compound represented by the above formula (D2EHIm_mMDI_Me) as a brown viscous liquid. The target product (main product) was analyzed by ion chromatography. 1 The H-NMR and mass spectrometry (LC-MS) results, as well as the mass spectrometry (LC-MS) results for three by-products, are shown below. (target object, main product)

[0204] [ka]

[0205] 1 H-NMR(CDCl3)δ(ppm)=7.43-7.06 (m, 8H), 6.86 (s, 2H), 4.47 (m, 4H), 2.36 (s, 3H), 2.12 (s, 2H), 1.86 (m, 2H), 1.31 (m, 16H), 0.91 (m, 12H) LC-MS:C 35 H 51 N4O2 + Calculated value = 559.4007, measured value (M + H + )=559.3976 (by-product)

[0206] [ka]

[0207] LC-MS:C 17 H 19 N2O2 + Calculated value = 283.1441, measured value (M + H + )=283.1426

[0208] [ka]

[0209] LC-MS:C 15 H 17 N2O + Calculated value = 241.1335, measured value (M + H + )=241.1325

[0210] [ka]

[0211] LC-MS:C 49 H 63 N6O3 + Calculated value = 783.4956, measured value (M + H + )=783.4919

[0212] Example 4 Synthesis of D2EHIm_crMDI_Me

[0213] [ka]

[0214] In the formula, X 1 ~X 3 At least one of the X groups is substituted with a group represented by (a), and the rest are substituted with a group represented by (b). 1 ~X 3 are all substituted with (a), or X 1 ~X 3Although the reaction mixture may contain a compound in which all of (a) and (b) are substituted, the main component of the reaction mixture is a compound substituted with at least one (a) and at least one (b). m is an integer of 0 to 4.

[0215] A 180 mL three-neck reactor purged with nitrogen was charged with 30.0 g of toluene and heated to reflux. Subsequently, a mixed solution of 30.0 g (purity: 0.075 mol) of [D2EHI][OAc] obtained in Production Example 1 and 30.0 g of toluene, and a mixed solution of 26.1 g (NCO group: 198.9 mmol) of polymeric MDI (Sumidur 44V20: NCO group content: 32.0%, manufactured by Sumika Covestro Urethane Co., Ltd.) and 24.0 g of toluene were added dropwise to the reactor over 2 hours and stirred for 1 hour. After stirring, the resulting reaction mixture was concentrated to dryness, yielding 48.6 g of a mixture containing the compound represented by the above formula (D2EHIm_crMDI_Me) as a brown solid. Tetralin was added to the resulting brown solid as an internal standard. 1 H-NMR analysis revealed that the concentration of amidate groups in the brown solid was 0.765 mmol / g, based on the hydrogen 4H of the methylene group adjacent to the nitrogen atom of the imidazolium group. 1 The results of H-NMR analysis are shown below. 1 H-NMR(CDCl3)δ(ppm)=7.41-6.88(m), 4.46-4.36(m)3.94-3.87(m), 2.12(s), 2.03-1.88(m), 1.38-1.10(m), 0.90-0.73(m)

[0216] Example 5 Synthesis of D2EHIm_crMDI_2EH

[0217] [ka]

[0218] In the formula, X 1 ~X 3 At least one of the X groups is substituted with a group represented by (a), and the rest are substituted with a group represented by (b). 1 ~X3 are all substituted with (a), or X 1 ~X 3 Although the reaction mixture may contain a compound in which all of (a) and (b) are substituted, the main component of the reaction mixture is a compound substituted with at least one (a) and at least one (b). m is an integer of 0 to 4. 30.0 g of toluene was charged into a 180 mL three-neck reactor purged with nitrogen and heated to reflux. Subsequently, a mixed solution of 30.0 g of [D2EHI][2EHA] (purity: 42.1 mmol) obtained in Production Example 2 and 30.0 g of toluene, and a mixed solution of 17.6 g of polymeric MDI (Sumidur 44V20: NCO group content: 32.0%, manufactured by Sumika Covestro Urethane Co., Ltd.) (NCO group: 134.1 mol) and 24.0 g of toluene were added dropwise to the reactor over 2 hours and stirred for 1 hour. After stirring, the resulting reaction mixture was concentrated to dryness to obtain 50.1 g of a mixture containing the compound represented by the above formula (D2EHIm_crMDI_2EH) as a brown solid. Tetralin was added to the resulting brown solid as an internal standard substance. 1 H-NMR analysis revealed that the concentration of amidate groups in the brown solid was 0.622 mmol / g, based on the hydrogen 4H of the methylene group adjacent to the nitrogen atom of the imidazolium group. 1 The results of H-NMR analysis are shown below. 1 H-NMR(CDCl3)δ(ppm)=7.50-6.89(m), 4.53-4.37(m)4.01-3.81(m), 2.13-2.05( m), 1.93-1.84(m), 1.76-1.65(m), 1.60-1.47(m), 1.40-1.28(m), 0.99-0.80(m)

[0219] Evaluation example 1 A MEKO (methyl ethyl ketone oxime) block product of the biuret-type HDI obtained in Production Example 5, polyester polyol (P-510, manufactured by Kuraray Co., Ltd.), and D2EHIm_TDI_Me obtained in Example 1 were added so that the composition of the thermosetting resin composition would be such that the ratio of available NCO groups (mol):hydroxyl groups (mol):amidate groups (mol) = 1.00:0.95:0.05, and methyl isobutyl ketone was added so that the total amount of solvent was 1.0 times the weight of the solid content of the blocked isocyanate, followed by stirring for 30 minutes to prepare a thermosetting resin composition.

[0220] Approximately 0.6 mL of the prepared thermosetting resin composition was added to the hot plate of an automatic curing time measuring device, which had been preheated to a predetermined temperature, and stirred. The curing time at each temperature was measured by counting the time when the stirring torque exceeded 20% (0.86 mN m). The results are shown in Table 2.

[0221] Evaluation Examples 2 to 5 A thermosetting resin composition was prepared and the curing time was measured in the same manner as in Evaluation Example 1, except that D2EHIm_TDI_Me was changed to an amidate compound shown in Table 2. The results are shown in Table 2.

[0222] Comparative Example 1 A thermosetting resin composition was prepared in the same manner as in Evaluation Example 1, except that D2EHIm_TDI_Me was replaced with dibutyltin dilaurate (hereinafter referred to as DBTDL) and the composition of the thermosetting resin composition was adjusted to have an effective NCO group (mol):hydroxyl group (mol):DBTDL (mol) ratio of 1.00:0.95:0.05, and the curing time was measured. The results are shown in Table 2.

[0223] [Table 2]

Claims

1. The following formula (1) 【Chemical 1】 (In the formula, R １ and R ４ are the same and represent a methyl group, an ethyl group, a butyl group, an octyl group, a 2-ethylhexyl group, or a benzyl group. ２ and R ３ are the same and represent a hydrogen atom. ５ represents a methyl group, an ethyl group, a heptyl group, or a 1-ethylpentyl group. and an imidazolium carboxylate represented by the following formula (2): 【Chemistry 2】 (In the formula, A represents a residue obtained by removing an isocyanate group from at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate; and x represents an integer of 2 or more and 20 or less.) The method includes a step of reacting a polyisocyanate compound represented by the following formula (3): 【Chemistry 3】 (In the formula, y and z are integers of 1 or more and 19 or less, and the sum of y and z is 2 or more and 20 or less. A, R １ , R ２ , R ３ , R ４ , R ５ are each as defined above.) A method for producing an amidate compound represented by the formula:

2. The method for producing an amidate compound according to claim 1, wherein R 1 and R 4 in the imidazolium carboxylate represented by formula (1) are the same and are 2-ethylhexyl groups.

3. The method for producing an amidate compound according to claim 1, wherein R 5 in the imidazolium carboxylate represented by formula (1) is a methyl group or a 1-ethylpentyl group.

4. Formula (3) 【Chemistry 4】 (In the formula, y and z are integers of 1 or more and 19 or less, and the sum of y and z is 2 or more and 20 or less. R １ and R ４ are the same and represent a methyl group, an ethyl group, a butyl group, an octyl group, a 2-ethylhexyl group, or a benzyl group. ２ and R ３ are the same and represent a hydrogen atom. ５ represents a methyl group, an ethyl group, a heptyl group, or a 1-ethylpentyl group. A represents a residue obtained by removing an isocyanate group from at least one polyisocyanate selected from the group consisting of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate. An amidate compound represented by the formula:

5. The amidate compound according to claim 4, wherein R 1 and R 4 of the amidate compound represented by formula (3) are the same and are 2-ethylhexyl groups.

6. The amidate compound according to claim 4, wherein R 5 of the amidate compound represented by formula (3) is a methyl group or a 1-ethylpentyl group.

7. A blocking agent dissociation catalyst for blocked isocyanates, comprising the amidate compound according to any one of claims 4 to 6.

8. A thermosetting resin composition comprising the amidate compound according to any one of claims 4 to 6, a blocked isocyanate, and a compound having an isocyanate-reactive group.

9. A cured product obtained by curing the thermosetting resin composition according to claim 8.

10. A method for producing a cured product, comprising the step of heating and curing the thermosetting resin composition according to claim 8.

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