Blocked polyisocyanate composition, thermosetting resin composition, cured product and method for producing the same

Abstract

The present invention provides a blocked polyisocyanate composition, which contains a blocked polyisocyanate compound and an amidate compound represented by the following formula (2). Formula (2): (In formula (2), B, R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 As defined in the specification.).

Description

Technical Field

[0001] The present invention relates to a blocked polyisocyanate composition, a thermosetting resin composition, a cured product and a method for producing the same. Background Art

[0002] A blocked polyisocyanate composition refers to a composition containing a blocked polyisocyanate compound and a dissociation catalyst for the blocking agent. A blocked polyisocyanate compound is a compound obtained by reacting a polyisocyanate compound with a blocking agent having an active hydrogen group capable of reacting with an isocyanate group. Blocked polyisocyanate compounds have the following properties: the isocyanate groups of the polyisocyanate are blocked by the blocking agent, thereby becoming inactivated at room temperature. However, the blocking agent dissociates upon heating, regenerating the isocyanate groups. Due to these properties, blocked polyisocyanate compositions are widely used in coatings, adhesives, and other applications as raw materials or crosslinking agents for one-component thermosetting polyurethane resins.

[0003] In recent years, curing at even lower temperatures has been required for the purpose of reducing energy costs and processing into resin materials with low heat resistance.

[0004] A catalyst may be added for the purpose of lowering the curing temperature. As compounds used as catalysts, tin compounds such as dibutyltin dilaurate (hereinafter referred to as DBTDL) are generally known.

[0005] The thermosetting resin composition containing the blocked polyisocyanate compound formed using the blocking agent and the tin compound generally requires a curing temperature of 120° C. or higher.

[0006] Furthermore, as a blocking agent dissociation catalyst, 1-methyl-3-n-octylimidazolium-2-N-phenylamide represented by the following structural formula is known (Patent Document 1).

[0007] [Chemical Formula 1]

[0008]

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: WO2019 / 065953A1 Summary of the Invention

[0012] Technical problem to be solved by the invention

[0013] The present inventors evaluated the curability of a thermosetting resin composition containing a blocked polyisocyanate blocked with methyl ethyl ketoxime and a polyol using 1-methyl-3-n-octylimidazolium-2-N-phenylamide described in Patent Document 1 as a blocking agent dissociation catalyst. The results showed that a temperature exceeding 100° C. was required to cure the composition within 30 minutes (Comparative Example 2 described below), and the low-temperature curability was unsatisfactory.

[0014] Therefore, an object of the present invention is to provide a blocked polyisocyanate composition having excellent low-temperature curability, a thermosetting resin composition containing the blocked polyisocyanate composition, and a cured product thereof.

[0015] Means for solving technical problems

[0016] The present invention provides the following blocked polyisocyanate composition, thermosetting composition, and cured product.

[0017] [1]

[0018] A blocked polyisocyanate composition contains a blocked polyisocyanate compound and an amidate compound represented by the following formula (2).

[0019] Formula (2):

[0020] [Chemical Formula 2]

[0021]

[0022] (In formula (2), B represents a substituted or unsubstituted hydrocarbon group, R 4 、R 5 、R 6 、R 9 、R 10 and R 11 are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a heteroatom. 7 and R 8 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a heteroatom. 4 and R 5 、R 5 and R 6 、R 7 and R 8 、R 9 and R 10 , or R 10 and R 11 can form a ring structure together with the carbon atom to which they are bonded; y is an integer from 1 to 20; CR 4 R 5 R 6 The group or CR shown 9 R10 R 11 The group shown is or is not adamantyl.)

[0023] [2]

[0024] The blocked polyisocyanate composition according to [1], wherein B in formula (2) is a substituted or unsubstituted aromatic hydrocarbon group.

[0025] 〔3〕

[0026] The blocked polyisocyanate composition according to [1] or [2], wherein R 4 、R 5 、R 9 and R 10 The same or different groups are hydrocarbon groups having 1 to 6 carbon atoms which may be substituted by a heteroatom.

[0027] [4]

[0028] The blocked polyisocyanate composition according to any one of [1] to [3], wherein R 6 and R 11 The same or different groups are hydrocarbon groups having 1 to 12 carbon atoms which may be substituted by a heteroatom.

[0029] 〔5〕

[0030] The blocked polyisocyanate composition according to any one of [1] to [4], wherein R 7 and R 8 A hydrogen atom.

[0031] [6]

[0032] The blocked polyisocyanate composition according to [1], wherein the amidated compound represented by formula (2) is any one of the five compounds represented by the following formulae.

[0033] [Chemical Formula 3]

[0034]

[0035] (In the formula, n is 0 or an integer from 1 to 4.)

[0036] [7]

[0037] The blocked polyisocyanate composition according to any one of [1] to [6], wherein the blocked polyisocyanate compound is a reaction product of a blocking agent and a polyisocyanate, and the blocking agent is an oxime-based blocking agent.

[0038] 〔8〕

[0039] The blocked polyisocyanate composition according to any one of [1] to [6], wherein the blocked polyisocyanate compound is a reaction product of a blocking agent and a polyisocyanate, and the blocking agent is methyl ethyl ketoxime.

[0040] 〔9〕

[0041] A thermosetting resin composition comprising the blocked polyisocyanate composition described in any one of [1] to [8] and a compound having an isocyanate-reactive group.

[0042]

[10]

[0043] The thermosetting resin composition according to [9], wherein the compound having an isocyanate-reactive group is a polyol compound.

[0044]

[11]

[0045] A cured product obtained by curing the thermosetting resin composition described in [9] or

[10] .

[0046]

[12]

[0047] A method for producing a cured product, comprising the step of heating the thermosetting resin composition according to [9] or

[10] to cure it.

[0048] Effects of the Invention

[0049] According to the present invention, there are provided a blocked polyisocyanate composition having excellent low-temperature curability, a thermosetting resin composition containing the blocked polyisocyanate composition, a cured product thereof, and a method for producing the cured product. DETAILED DESCRIPTION

[0050] <Blocked polyisocyanate composition containing a blocked polyisocyanate compound and an amidated compound represented by formula (2)>

[0051] The blocked polyisocyanate composition of the present invention contains a blocked polyisocyanate compound and an amidate compound represented by formula (2).

[0052] The blocked polyisocyanate compound will be described.

[0053] Examples of blocked polyisocyanate compounds include compounds obtained by reacting polyisocyanate with a blocking agent to block the isocyanate groups in the polyisocyanate. The blocked polyisocyanate compounds may be used alone or in combination of two or more.

[0054] The polyisocyanate constituting the blocked polyisocyanate compound is not particularly limited as long as it is a compound having two or more isocyanate groups. Examples of the polyisocyanate include the following polyisocyanates.

[0055] (i) aliphatic polyisocyanates,

[0056] (ii) alicyclic polyisocyanates,

[0057] (iii) aromatic polyisocyanates,

[0058] (iv) aromatic aliphatic polyisocyanates,

[0059] (v) A modified isocyanate formed from at least one selected from aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and aromatic aliphatic polyisocyanates.

[0060] Preferred isocyanates are modified isocyanates formed from at least one selected from the group consisting of (i) aliphatic polyisocyanates, (ii) alicyclic polyisocyanates, and (v) aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

[0061] These polyisocyanates may be used alone or in combination of two or more.

[0062] Examples of the aliphatic polyisocyanate include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate.

[0063] Examples of the alicyclic polyisocyanate include 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, 3-isocyanatemethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate (IPDI)), bis-(4-isocyanatecyclohexyl)methane, and norbornane diisocyanate.

[0064] Examples of the aromatic polyisocyanate include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate biphenyl, 3,3′-dimethyl-4,4′-diisocyanate diphenylmethane, and 1,5-naphthalene diisocyanate.

[0065] Examples of the aromatic aliphatic polyisocyanate include 1,3-xylylenediisocyanate, 1,4-xylylenediisocyanate, and α,α,α′,α′-tetramethylxylylenediisocyanate.

[0066] Examples of the modified isocyanate include isocyanate-terminated compounds obtained by reacting the above-mentioned polyisocyanate compounds with a compound having an active hydrogen group, reaction products of polyisocyanate compounds or / and such isocyanate-terminated compounds (e.g., addition-type polyisocyanates, isocyanate-modified products based on allophanation reaction, carbodiimidation reaction, uretdione reaction, isocyanuration reaction, uretonimation reaction, biuret reaction, etc.), and are preferably addition-type polyisocyanates, polyisocyanates modified by isocyanuration reaction, and polyisocyanates modified by biuret reaction (polyisocyanates having a biuret bond).

[0067] Polyisocyanates having biuret bonds are obtained by reacting a so-called biuretizing agent, such as water, tert-butyl alcohol, or urea, with a polyisocyanate at a molar ratio of biuretizing agent to isocyanate groups of the polyisocyanate of approximately 1 / 2 to 1 / 100, followed by removal of unreacted polyisocyanate compounds and purification. Polyisocyanates having isocyanurate bonds can be obtained, for example, by undergoing a cyclic trimerization reaction using a catalyst, terminating the reaction when the conversion reaches approximately 5 to 80% by mass, removing unreacted polyisocyanates, and purifying the reaction. In this case, monovalent to hexavalent alcohol compounds may be used in combination.

[0068] Examples of polyisocyanates having a biuret bond include biuret-modified 1,6-hexamethylene diisocyanate (HDI), biuret-modified isophorone diisocyanate (IPDI), and biuret-modified toluene diisocyanate (TDI) shown below. Commercially available products include Desmodur N75, Desmodur N100, and Desmodur N3200 manufactured by Sumika Covestro Urethane Co., Ltd., and DURANATE 24A-100, DURANATE 22A-75P, and DURANATE 21S-75E manufactured by Asahi Kasei Corporation.

[0069] [Chemical Formula 4]

[0070]

[0071] Polyisocyanates having isocyanurate bonds are obtained, for example, by carrying out a cyclic trimerization reaction using a catalyst, stopping the reaction when the conversion rate reaches about 5 to about 80% by mass, removing the unreacted polyisocyanate, and purifying the obtained products. In this case, a monovalent to hexavalent alcohol compound may be used in combination.

[0072] As the catalyst for the isocyanuration reaction, a basic catalyst is generally preferred.

[0073] Examples of the catalyst include (1) to (8), and two or more of these catalysts may be used in combination.

[0074] (1) Hydroxides of tetraalkylammonium such as tetramethylammonium, tetraethylammonium, and trimethylbenzylammonium, and weak organic acid salts such as acetic acid and decanoic acid;

[0075] (2) Hydroxylalkylammonium hydroxides such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium, and organic weak acid salts such as acetic acid and decanoic acid;

[0076] (3) Metal salts of alkyl carboxylic acids such as tin, zinc, lead, etc.;

[0077] (4) Metal alkoxides such as sodium and potassium;

[0078] (5) Compounds containing aminosilyl groups such as hexamethyldisilazane;

[0079] (6) Mannich bases;

[0080] (7) Combination of tertiary amines and epoxy compounds;

[0081] (8) Phosphorus compounds such as tributylphosphine.

[0082] If the catalyst may adversely affect the physical properties of the coating or coating film, the catalyst may be neutralized with an acidic compound. Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphorous acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, methyl p-toluenesulfonate, and ethyl p-toluenesulfonate, or their derivatives; ethyl phosphate, diethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, di(2-ethylhexyl) phosphate, isodecyl phosphate, diisodecyl phosphate, oleyl alcohol phosphate, tetradecyl acid phosphate, ethylene glycol acid phosphate, butyl pyrophosphate, and butyl phosphite. Two or more of these compounds may be used in combination.

[0083] Examples of the polyisocyanate having an isocyanurate bond include the isocyanurate-modified HDI, the isocyanurate-modified IPDI, and the isocyanurate-modified TDI shown below. Commercially available products include Sumidur N3300, Desmodur 3900, Desmodur Z4470BA, Desmodur XP2763, Desmodur IL1351BA, and Desmodur HLBA manufactured by Sumika Covestro Urethane Co., Ltd., and DURANATE TPA-100, DURANATE MFA-75B, DURANATE TUL-100, and DURANATE TSA-100 manufactured by Asahi Kasei Corporation.

[0084] [Chemical Formula 5]

[0085]

[0086] Polyisocyanates having urethane bonds can be obtained, for example, by reacting a divalent to hexavalent alcohol compound such as trimethylolpropane (hereinafter referred to as TMP) with a diisocyanate at a molar ratio of about 1 / 2 to about 1 / 100 of the hydroxyl group of the alcohol compound to the isocyanate group of the polyisocyanate, followed by removal of the unreacted polyisocyanate and purification. Removal of the unreacted polyisocyanate and purification are not necessarily required.

[0087] Examples of polyisocyanates having a urethane bond include reaction products of HDI and TMP, reaction products of IPDI and TMP, and reaction products of TDI and TMP shown below. Commercially available products include Sumidur N3300, Desmodur 3900, Desmodur Z4470BA, Desmodur XP2763, Desmodur IL1351BA, and Desmodur HLBA manufactured by Sumika Covestro Urethane Co., Ltd., and DURANATE TPA-100, DURANATE MFA-75B, DURANATE TUL-100, and DURANATE TSA-100 manufactured by Asahi Kasei Corporation.

[0088] [Chemical Formula 6]

[0089]

[0090] Examples of known blocking agents for isocyanates in which a part of the isocyanate groups of the polyisocyanates and modified isocyanates are blocked with known blocking agents include phenols such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tert-amyl alcohol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether; Alcohols such as benzyl alcohol, pyrazoles such as 3,5-dimethylpyrazole and 1,2-pyrazole, triazoles such as 1,2,4-triazole, halogen-substituted alcohols such as chloroethanol and 1,3-dichloro-2-propanol, lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam, active methylene compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate, in addition to these, amines, imides, thiols, imines, ureas, diaryls, and the like can be mentioned.

[0091] Examples of the end-capping agent include alcohol compounds, phenol compounds, amine compounds, lactam compounds, oxime compounds, active methylene compounds, pyrazole compounds, and triazole compounds. Lactam compounds, oxime compounds, and pyrazole compounds are preferred. Oxime compounds are particularly preferred because they can be dissociated in a short time even at low temperatures such as below 100°C by combining with the amide compound represented by formula (2).

[0092] Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tert-amyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol.

[0093] Examples of the phenolic compound include phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, chlorophenol, and 2-hydroxypyridine.

[0094] Examples of the amine compound include diisopropylamine and the like.

[0095] Examples of the lactam compound include ε-caprolactam, δ-valerolactam, and γ-butyrolactam, and ε-caprolactam is preferred.

[0096] Preferred examples of the oxime compound include compounds represented by the following formula (B).

[0097] Formula (B):

[0098] HO-N=R(B)

[0099] (In formula (B), R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

[0100] R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0101] Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, 1-methylpropyl, pentyl, hexyl, heptyl, octyl, 1-ethylpentyl, nonyl, 2-ethylhexyl, undecyl, tridecyl, pentadecyl, and heptadecyl.

[0102] Specific examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, and the like, with methyl ethyl ketone oxime being preferred.

[0103] Examples of the pyrazole compound include 1,2-pyrazole and 3,5-dimethylpyrazole. Examples of the triazole compound include 1,2,4-triazole, and 3,5-dimethylpyrazole is preferred.

[0104] Examples of the active methylene compounds include methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, and ethyl malonate.

[0105] The amide compound represented by formula (2) (hereinafter referred to as amide compound (2)) will be described.

[0106] Formula (2):

[0107] [Chemical Formula 7]

[0108]

[0109] (In formula (2), B represents a substituted or unsubstituted hydrocarbon group, R 4 、R 5 、R 6 、R 9 、R 10 and R 11 are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a heteroatom. 7 and R 8 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a heteroatom. 4 and R 5 、R 5 and R 6 、R 7 and R 8 、R 9 and R 10 , or R 10 and R 11They can form a ring structure together with the carbon atoms to which they are bonded. y is an integer of 1 to 20. 4 R 5 R 6 A group represented by CR 9 R 10 R 11 The group represented by may be an adamantyl group.)

[0110] In one embodiment, in formula (2), B is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. In another embodiment, B is a substituted or unsubstituted aromatic hydrocarbon group, preferably a substituted or unsubstituted aromatic hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted aromatic hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted aromatic hydrocarbon group having 1 to 30 carbon atoms.

[0111] In this specification, the term "substituted or unsubstituted hydrocarbon group" includes (i) a hydrocarbon group that may have a substituent, (ii) a hydrocarbon group that may be substituted with a heteroatom, and (iii) a hydrocarbon group that has a substituent and is substituted with a heteroatom. Furthermore, the term "substituted or unsubstituted aromatic hydrocarbon group" includes (iv) an aromatic hydrocarbon group that may have a substituent, (v) an aromatic hydrocarbon group that may be substituted with a heteroatom, and (vi) an aromatic hydrocarbon group that has a substituent and is substituted with a heteroatom.

[0112] In B, examples of the unsubstituted hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, dodecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl, tolyl, and allyl.

[0113] When B is a hydrocarbon group having a substituent, examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkylamino groups such as methylamino; dialkylamino groups such as dimethylamino; alkoxy groups such as methoxy and ethoxy; aryloxy groups such as phenoxy and naphthyloxy; aralkyloxy groups such as benzyloxy and naphthylmethoxy; haloalkyl groups such as trifluoromethyl; nitro, cyano, sulfonyl, alkylcarbonylamino, alkoxycarbonylamino, (alkylamino)carbonylamino, or (dialkylamino)carbonylamino. Furthermore, the hydrocarbon group of B may be substituted with at least one heteroatom such as an oxygen atom, nitrogen atom, or sulfur atom. When the hydrocarbon group of B is substituted with at least one heteroatom such as an oxygen atom, nitrogen atom, or sulfur atom, the hydrocarbon group may have, for example, at least one group such as -O-, -N<, -NH-, -S-, or -SO2-, and the hydrocarbon chain may be interrupted by such a group.

[0114] Examples of the alkyl moiety of the alkylamino, dialkylamino, alkoxy, haloalkyl, alkylcarbonylamino, alkoxycarbonylamino, (alkylamino)carbonylamino, and (dialkylamino)carbonylamino groups include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, heptyl, octyl, and 2-ethylhexyl. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms.

[0115] Examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms. Specific examples of the aryl moiety include phenyl and naphthyl.

[0116] Examples of the aralkyl moiety of the aralkyloxy group include aralkyl groups having 7 to 12 carbon atoms. Specific examples of the aralkyl moiety include benzyl and naphthylmethyl groups.

[0117] The number of substituents may be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0118] R 7 and R 8 The same or different groups represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a heteroatom, preferably a hydrogen atom.

[0119] y is an integer of 1 to 20, preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 or 2.

[0120] R 4 、R 5 、R 6 、R 9 、R 10 and R 11 The hydrocarbon groups are the same or different and are 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, more preferably hydrocarbon groups having 1 to 12 carbon atoms which may be substituted with a heteroatom, further preferably hydrocarbon groups having 1 to 6 carbon atoms which may be substituted with a heteroatom, and particularly preferably hydrocarbon groups having 1 to 4 carbon atoms which may be substituted with a heteroatom. Examples of the hydrocarbon group include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, octyl, benzyl, and phenyl. Preferred are methyl, ethyl, neopentyl, and phenyl, and more preferably methyl and neopentyl.

[0121] Alternatively, R 4 、R 5 、R 9 、R 10 The same or different, preferably a hydrocarbon group having 1 to 4 carbon atoms which may be substituted by a heteroatom, R6 、R 11 The groups are the same or different and preferably are hydrocarbon groups having 1 to 12 carbon atoms which may be substituted with a heteroatom.

[0122] R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 Together with the carbon atoms to which they are bonded, they may form ring structures.

[0123] R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 When they form a ring structure together with the carbon atom to which they are bonded, for example, a benzimidazolium ring structure represented by the following formula (2x) can be employed.

[0124] [Chemical Formula 8]

[0125]

[0126] (In formula (2x), B, R 4 、R 5 、R 6 、R 9 、R 10 、R 11 and y are as defined above. w 、R x 、R y and R z Each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, CR 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group.)

[0127] In addition, by CR 4 R 5 R 6 The group shown, represented by CR 9 R 10 R 11 The group shown may be an adamantyl group, for example, a 1-adamantyl group shown in the following formula (IV).

[0128] [Chemical Formula 9]

[0129]

[0130] In the case of having a 1-adamantyl group as represented by formula (IV), for example, a structure having a 1-adamantyl group as represented by the following formula (2y) can be employed.

[0131] [Chemical Formula 10]

[0132]

[0133] (In formula (2y), B, R 7 、R 8 and y are as defined above.)

[0134] The amidate compound represented by formula (2) is preferably an amidate compound represented by any one of formula (2-1), formula (2-2) and formula (2-3).

[0135] Formula (2-1):

[0136] [Chemical Formula 11]

[0137]

[0138] (In formula (2-1), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 As defined above. 4 R 5 R 6 The group shown, represented by CR 9 R 10 R 11 The group shown may be an adamantyl group. 12 represents a substituted or unsubstituted hydrocarbon group.)

[0139] Formula (2-2):

[0140] [Chemical Formula 12]

[0141]

[0142] (In formula (2-2), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R11 As defined above. 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group. 13 represents a substituted or unsubstituted divalent hydrocarbon group.)

[0143] Formula (2-3):

[0144] [Chemical Formula 13]

[0145]

[0146] (In formula (2-3), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 As defined above. 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group. 1 、E 2 and E 3 Each independently represents a substituted or unsubstituted hydrocarbon group, a halogen atom, an alkylamino group, a dialkylamino group, an alkoxy group, an aryloxy group, an aralkyloxy group, a nitro group, a cyano group, a sulfonyl group, an (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group, or an isocyanate group. f and g each independently represent an integer from 0 to 4. a and b are each 0 or 1, and c, d, and e each independently represent an integer from 0 to 4. When f is 0, at least one of a or b is 1.

[0147] In formula (2-1), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 As defined above. 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group.

[0148] R 12 It is a substituted or unsubstituted hydrocarbon group, preferably a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, decyl, dodecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl, tolyl, and allyl groups, with benzyl and phenyl being preferred.

[0149] R 12 When the substituent has a substituent, examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine, alkylamino groups such as methylamino, dialkylamino groups such as dimethylamino, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy and naphthyloxy, aralkyloxy groups such as benzyloxy and naphthylmethoxy, halogenated alkyl groups such as trifluoromethyl, nitro, cyano, sulfonyl, alkylcarbonylamino, alkoxycarbonylamino, (alkylamino)carbonylamino, (dialkylamino)carbonylamino, and isocyanate groups. In addition, R 12 The hydrocarbon group may be substituted by at least one heteroatom selected from oxygen, nitrogen, sulfur, etc. When the hydrocarbon group is substituted by at least one heteroatom selected from oxygen, nitrogen, sulfur, etc., the hydrocarbon group may have at least one group selected from -O-, -N<, -NH-, -S-, -SO2-, etc., and the hydrocarbon chain may be interrupted by these groups. 12 When the compound has a substituent, the number of the substituents is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.

[0150] Examples of the alkyl moiety of the alkylamino, dialkylamino, alkoxy, haloalkyl, alkylcarbonylamino, alkoxycarbonylamino, (alkylamino)carbonylamino, and (dialkylamino)carbonylamino groups include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, heptyl, octyl, and 2-ethylhexyl. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms.

[0151] Examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms. Specific examples of the aryl moiety include phenyl and naphthyl.

[0152] Examples of the aralkyl moiety of the aralkyloxy group include aralkyl groups having 7 to 12 carbon atoms. Specific examples of the aralkyl moiety include benzyl and naphthylmethyl groups.

[0153] The number of substituents may be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0154] R 12 Preferred are hydrocarbon groups that may be substituted with halogen atoms or hydrocarbon groups that may be substituted with hetero atoms. More preferred are hydrocarbon groups having 1 to 50 carbon atoms that may be substituted with halogen atoms or hydrocarbon groups having 1 to 50 carbon atoms that may be substituted with hetero atoms. Further preferred are hydrocarbon groups having 1 to 30 carbon atoms that may be substituted with halogen atoms or hydrocarbon groups having 1 to 30 carbon atoms that may be substituted with hetero atoms. Particularly preferred are hydrocarbon groups having 1 to 12 carbon atoms that may be substituted with halogen atoms or hydrocarbon groups having 1 to 12 carbon atoms that may be substituted with hetero atoms. Furthermore, preferred hydrocarbon groups are aromatic hydrocarbon groups such as aryl groups and aralkyl groups.

[0155] R 12 In the example, examples of the hydrocarbon group substituted with a halogen atom include chlorophenyl and the like.

[0156] R 12 In the example of the heteroatom-substituted hydrocarbon group having 1 to 20 carbon atoms, there can be mentioned 2-methoxymethyl, 2-ethoxymethyl, 2-(dimethylamino)methyl and the like.

[0157] In formula (2-2), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 As defined above. 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group.

[0158] R 13It is a substituted or unsubstituted divalent hydrocarbon group, preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 100 carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 50 carbon atoms, and particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 30 carbon atoms. Specific examples 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-diylbimethylene, and cyclohexane-1,4-diylbimethylene; arylene groups such as m-phenylene, p-phenylene, 2-methyl-m-phenylene, 4-methyl-m-phenylene, and naphthylene; arylalkylene groups such as phenylethylene, 1-phenylpropylene, 2-phenylpropylene, 1-phenylbutylene, 2-phenylbutylene, naphthylmethylene, and naphthylethylene; arylenealkylene groups such as p-xylylene formed by appropriately combining the above alkylene and arylene groups; and alkylenearylene groups such as methylenediphenylene and polymethylenepolyphenylene. These divalent hydrocarbon groups may be repeated or combined to form a single divalent hydrocarbon group.

[0159] R 13 When the divalent hydrocarbon group of has a substituent, examples of the substituent include halogen atoms such as fluorine, chlorine, bromine, and iodine, alkylamino groups such as methylamino, dialkylamino groups such as dimethylamino, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy and naphthyloxy, aralkyloxy groups such as benzyloxynaphthylmethoxy, halogenated alkyl groups such as trifluoromethyl, nitro, cyano, sulfonyl, (alkylamino)carbonylamino, (dialkylamino)carbonylamino, and isocyanate groups. In addition, R 13 The hydrocarbon group may be substituted by at least one heteroatom selected from oxygen, nitrogen, sulfur, etc. When the hydrocarbon group is substituted by at least one heteroatom selected from oxygen, nitrogen, sulfur, etc., the hydrocarbon group may have at least one group selected from -O-, -N<, -NH-, -S-, -SO2-, etc., and the hydrocarbon chain may be interrupted by these groups. 13 When the compound has a substituent, the number of the substituents is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.

[0160] R 13 Preferred are divalent hydrocarbon groups which may be substituted with halogen atoms or divalent hydrocarbon groups which may be substituted with hetero atoms. Among them, divalent hydrocarbon groups having 1 to 50 carbon atoms which may be substituted with halogen atoms or divalent hydrocarbon groups having 1 to 50 carbon atoms which may be substituted with hetero atoms are more preferred, divalent hydrocarbon groups having 1 to 30 carbon atoms which may be substituted with halogen atoms or divalent hydrocarbon groups having 1 to 30 carbon atoms which may be substituted with hetero atoms are further preferred, and divalent hydrocarbon groups having 1 to 12 carbon atoms which may be substituted with halogen atoms or divalent hydrocarbon groups having 1 to 12 carbon atoms which may be substituted with hetero atoms are particularly preferred.

[0161] Examples of the alkyl moiety of the alkylamino, dialkylamino, alkoxy, haloalkyl, alkylcarbonylamino, alkoxycarbonylamino, (alkylamino)carbonylamino, and (dialkylamino)carbonylamino groups include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, heptyl, octyl, and 2-ethylhexyl. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms.

[0162] Examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms. Specific examples of the aryl moiety include phenyl and naphthyl.

[0163] Examples of the aralkyl moiety of the aralkyloxy group include aralkyl groups having 7 to 12 carbon atoms. Specific examples of the aralkyl moiety include benzyl and naphthylmethyl groups.

[0164] The number of substituents may be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0165] In formula (2-3), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 As defined above. 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group.

[0166] E 1 、E 2 and E 3 Each independently represents a substituted or unsubstituted hydrocarbon group, a halogen atom, an alkylamino group, a dialkylamino group, an alkoxy group, an aryloxy group, an aralkyloxy group, a nitro group, a cyano group, a sulfonyl group, an (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group or an isocyanate group, preferably a hydrocarbon group which may be substituted with a halogen atom, a hydrocarbon group which may be substituted with a heteroatom, an (alkylamino)carbonylamino group, a (dialkylamino)carbonylamino group or an isocyanate group, more preferably an (alkylamino)carbonylamino group or a (dialkylamino)carbonylamino group.

[0167] In E 1 、E 2 or E 3In the case of a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydrocarbon group having 1 to 50 carbon atoms is preferred, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms is more preferred, and a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms is further preferred.

[0168] E 1 、E 2 or E 3 In the case of a hydrocarbon group having a substituent, examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, alkylamino groups such as a methylamino group, dialkylamino groups such as a dimethylamino group, alkoxy groups such as a methoxy group and an ethoxy group, aralkyloxy groups such as a benzyloxy group, haloalkyl groups such as a trifluoromethyl group, a nitro group, a cyano group, a sulfonyl group, an alkylcarbonylamino group, an alkoxycarbonylamino group, a carbonylamino group such as an (alkylamino)carbonylamino group, and a (dialkylamino)carbonylamino group.

[0169] In addition, E 1 、E 2 or E 3 The hydrocarbon group may be substituted by at least one heteroatom selected from oxygen, nitrogen, sulfur, etc. 1 、E 2 or E 3 When the hydrocarbon group is substituted with at least one hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has at least one group such as -O-, -N<, -NH-, -S-, or -SO2-, and the hydrocarbon chain is interrupted by these groups.

[0170] Examples of the alkyl moiety of the alkylamino, dialkylamino, alkoxy, haloalkyl, alkylcarbonylamino, alkoxycarbonylamino, (alkylamino)carbonylamino, and (dialkylamino)carbonylamino groups include linear or branched alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 1-ethylpentyl, heptyl, octyl, and 2-ethylhexyl. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms.

[0171] Examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms. Specific examples of the aryl moiety include phenyl and naphthyl.

[0172] Examples of the aralkyl moiety of the aralkyloxy group include aralkyl groups having 7 to 12 carbon atoms. Specific examples of the aralkyl moiety include benzyl and naphthylmethyl groups.

[0173] The number of substituents may be 1 to 5, preferably 1 to 3, and more preferably 1 or 2.

[0174] In E 1 、E2 or E 3 In the case of a hydrocarbon group which may be substituted by a halogen atom or a hydrocarbon group which may be substituted by a heteroatom, it is preferably a hydrocarbon group having 1 to 50 carbon atoms which may be substituted by a halogen atom or a hydrocarbon group having 1 to 50 carbon atoms which may be substituted by a heteroatom, more preferably a hydrocarbon group having 1 to 30 carbon atoms which may be substituted by a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms which may be substituted by a heteroatom, and particularly preferably a hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a heteroatom.

[0175] In addition, the hydrocarbon group which may be substituted with a halogen atom or a hydrocarbon group which may be substituted with a heteroatom is preferably an aromatic hydrocarbon group such as an aryl group or a vinyl group. Specific examples of the hydrocarbon group which may be substituted with a halogen atom or a hydrocarbon group 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, a decyl group, a dodecyl group, an octadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a phenylnaphthyl group, a benzyl group, a phenethyl group, a tolyl group, and an allyl group, with benzyl group and a phenyl group being preferred.

[0176] As E 1 、E 2 or E 3 In the case of a hydrocarbon group which may be substituted with a halogen atom, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. 1 、E 2 and E 3 The hydrocarbon group can be substituted by heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms. 1 、E 2 or E 3 When the hydrocarbon group is substituted with at least one hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, the hydrocarbon group has at least one group such as -O-, -N<, -NH-, -S-, or -SO2-, and the hydrocarbon chain is interrupted by these groups.

[0177] E 1 、E 2 or E 3 In the example, examples of the hydrocarbon group substituted with a halogen atom include chlorophenyl and the like.

[0178] E 1 、E 2 or E 3 In the example of the heteroatom-substituted hydrocarbon group having 1 to 20 carbon atoms, there can be mentioned 2-methoxymethyl, 2-ethoxymethyl, 2-(dimethylamino)methyl and the like.

[0179] E 1 、E 2 and E 3When each independently represents a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0180] As E 1 、E 2 and E 3 In the case of an alkylamino group, a dialkylamino group, an alkoxy group, a (alkylamino)carbonylamino group, or a (dialkylamino)carbonylamino group, the alkyl moiety includes a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. The alkyl group preferably has 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms.

[0181] In E 1 、E 2 and E 3 In the case of an aryloxy group, examples of the aryl moiety of the aryloxy group include aryl groups having 6 to 10 carbon atoms. Specific examples of the aryl moiety include phenyl and naphthyl.

[0182] In E 1 、E 2 and E 3 In the case of an aralkyloxy group, examples of the aralkyl portion of the aralkyloxy group include aralkyl groups having 7 to 12 carbon atoms. Specific examples of the aralkyl portion include benzyl and naphthylmethyl groups.

[0183] f and g each independently represent an integer of 0 to 4. a and b each independently represent an integer of 0 to 4. c, d, and e each independently represent an integer of 0 to 4. When f is 0, at least one of a or b is 1.

[0184] Examples of the amidate compound (2) include the following compounds: tBu represents a tert-butyl group, tOct represents a 1,1,3,3-tetramethylbutyl group, 1Ad represents a 1-adamantyl group, Me represents a methyl group, Hept represents a heptyl group, and 1EtPent represents a 1-ethylpentyl group.

[0185] [Chemical Formula 14]

[0186]

[0187] [Chemical Formula 15]

[0188]

[0189]

[0190] [Chemical Formula 16]

[0191]

[0192] [Chemical Formula 17]

[0193]

[0194]

[0195] In formulas (2-1-28) to (2-1-36), n is an integer of 0 to 4.

[0196] [Chemical Formula 18]

[0197]

[0198]

[0199] [Chemical Formula 19]

[0200]

[0201]

[0202] [Chemical Formula 20]

[0203]

[0204] In formulas (2-3-1) to (2-3-3), n is an integer of 0 to 4.

[0205] The amidate compound (2) is preferably a compound represented by the formula (2-1-1) to (2-1-6), (2-1-7), (2-1-9), (2-1-10), (2-1-12), (2-1-13), (2-1-15), (2-1-37) to (2-1-45), (2-2-1) to (2-2-3), and (2-3-1) to (2-3-3), and more preferably a compound represented by the formula (2-1-1), (2-1-2), and (2-3-2).

[0206] The amidate compound (2) can be produced, for example, by the method shown below.

[0207] (Method 1) An imidazolium carboxylate represented by formula (5) is reacted with a carbonate represented by formula (6) (Reaction 1), and the resulting reaction product is reacted with an isocyanate compound represented by formula (10) (Reaction 2).

[0208] (Method 2) Method of reacting an imidazolium carboxylate with an isocyanate compound

[0209] (Method 3) A method described in Patent Document 1 in which an imidazolium-2-carboxylate compound is reacted with an isocyanate compound.

[0210] (Method 4) A method of reacting an imidazolium-2-ylidene compound with an isocyanate compound, as described in Stacul Chemistry 2013, Vol. 24, pp. 2059-2068.

[0211] Hereinafter, (Method 1) will be described.

[0212] (Reaction 1)

[0213] An imidazolium carboxylate represented by the following formula (5) (hereinafter referred to as imidazolium carboxylate (5)) is reacted with a carbonate represented by the following formula (6) (hereinafter referred to as carbonate (6)).

[0214] [Chemical Formula 21]

[0215]

[0216] (In formula (5), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 Each as defined above, CR 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group. 14 represents a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a hydrogen atom or a heteroatom.

[0217] Formula (6):

[0218] [Chemical Formula 22]

[0219]

[0220] (In formula (6), R 15 and R 16 are the same or different, and represent a hydrocarbon group having 1 to 6 carbon atoms, R 15 and R 16 Together with the oxygen atoms to which they are bonded, they can form ring structures.)

[0221] (Reaction 2)

[0222] Next, the obtained reaction product is reacted with an isocyanate compound represented by the following formula (10) in the presence of a solvent as needed to produce an amide compound (2).

[0223] Formula (10):

[0224] [Chemical Formula 23]

[0225]

[0226] (In formula (10), B and y are each as defined above.)

[0227] The imidazolium carboxylate (5) will be described.

[0228] In formula (5), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 and R 11 Each is as defined above. 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group.

[0229] R 14 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with 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. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a heteroatom include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 1-ethylpentyl, nonyl, 2-ethylhexyl, undecyl, tridecyl, pentadecyl, heptadecyl, vinyl, allyl, benzyl, cyclohexyl, adamantyl, and phenyl. Preferred examples include methyl, ethyl, propyl, isopropyl, butyl, heptyl, cyclohexyl, 1-ethylpentyl, and phenyl, and particularly preferred examples include methyl, ethyl, heptyl, and 1-ethylpentyl.

[0230] R 14In the example, heteroatoms include nitrogen, oxygen, and sulfur atoms. When a hydrocarbon group is substituted with at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, the hydrocarbon group may have, for example, at least one group selected from -O-, -N<, -NH-, -S-, and -SO2-, and the hydrocarbon chain may be interrupted by such a group. When a hydrocarbon group is substituted with at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, it is preferred that the hydrocarbon group be substituted with an oxygen atom and the hydrocarbon chain be interrupted by an -O- group. Alternatively, when a hydrocarbon group is substituted with at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, a hydrocarbon group may be formed having a group selected from -OH and -NH2.

[0231] R 14 In the example of the heteroatom-substituted hydrocarbon group having 1 to 20 carbon atoms, there can be mentioned 2-methoxymethyl, 2-ethoxymethyl, 2-(dimethylamino)methyl and the like.

[0232] In formula (5), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 When two adjacent groups in form a ring structure together with the carbon atom to which they are bonded, for example, the benzimidazolium ring structure (5x) shown below can be employed.

[0233] [Chemical Formula 24]

[0234]

[0235] (In formula (5x), R 4 、R 5 、R 6 、R 9 、R 10 、R 11 、R 14 、R w 、R x 、R y and R z Each is as defined above.)

[0236] In addition, in formula (5), CR 4 R 5 R 6 The groups shown, CR 9 R 10 R 11 The group shown may be an adamantyl group. In this case, for example, the structure (5y) having a 1-adamantyl group shown below can be adopted.

[0237] [Chemical Formula 25]

[0238]

[0239] (In formula (5y), R 7 、R 8 and R 14 Each is as defined above.)

[0240] Examples of the imidazolium carboxylate (5) include 1,3-di-tert-butylimidazolium formate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium formate, and 1,3-bis(1-adamantyl)imidazolium formate;

[0241] 1,3-di-tert-butylimidazolium acetate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate, 1,3-bis(1-adamantyl)imidazolium acetate;

[0242] 1,3-di-tert-butylimidazolium 2-ethylhexanoate, 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium 2-ethylhexanoate, 1,3-bis(1-adamantyl)imidazolium 2-ethylhexanoate, etc. Preferred examples include 1,3-di-tert-butylimidazolium acetate and 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate.

[0243] A commercially available imidazolium carboxylate (5) can be used. An imidazolium carboxylate obtained by a known method can be used as the imidazolium carboxylate (5). Alternatively, an imidazolium carboxylate produced by the method described below can be used.

[0244] The imidazolium carboxylate of formula (5) is obtained by reacting a dicarbonyl compound represented by formula (7), amine compounds represented by formula (8x) and formula (8y), formaldehyde, and a carboxylic acid represented by formula (9).

[0245] Formula (7):

[0246] [Chemical Formula 26]

[0247]

[0248] (In formula (7), R 7 and R 8 As defined above.)

[0249] Formula (8x):

[0250] [Chemical Formula 27]

[0251]

[0252] (In formula (8x), R 4 、R 5and R 6 As defined above. 4 R 5 R 6 The group shown may be an adamantyl group.)

[0253] Formula (8y):

[0254] [Chemical Formula 28]

[0255]

[0256] (In formula (8y), R 9 、R 10 and R 11 As defined above. 9 R 10 R 11 The group shown may be an adamantyl group.)

[0257] Formula (9):

[0258] [Chemical Formula 29]

[0259]

[0260] (In formula (9), R 14 As defined above.)

[0261] As the dicarbonyl compound represented by formula (7) (hereinafter referred to as dicarbonyl compound (7)), preferably, glyoxal, diacetyl (Japanese: ジアセチル), 3,4-hexanedione, 2,3-pentanedione, 2,3-heptanedione, 5-methyl-2,3-hexanedione, 3-methyl-2,3-cyclopentanedione, 1,2-cyclohexanedione, 1-phenyl-1,2-propanedione, and dibenzoyl are mentioned, more preferably, glyoxal and diacetyl are mentioned, and glyoxal is more preferred.

[0262] As the amine compounds represented by the formula (8x) and the formula (8y), amine compounds represented by the following formula (8ax) and the formula (8ay) are preferred, respectively.

[0263] Examples of the amine compound represented by formula (8x) (hereinafter referred to as amine compound (8x)) and the amine compound represented by formula (8y) (hereinafter referred to as amine compound (8y)) include tert-butylamine, 1,1,3,3-tetramethylbutylamine, and 1-adamantylamine, with 1,1,3,3-tetramethylbutylamine being preferred.

[0264] As the carboxylic acid represented by formula (9) (hereinafter referred to as carboxylic acid (9)), formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, lauric acid, tetradecanoic acid, palmitic acid, octadecanoic acid, cyclohexaneic acid, ethoxyacetic acid, propoxyacetic acid, 2-(2-methoxyethoxy)acetic acid, 2-(2-ethoxyethoxy)acetic acid, 2-(2-propoxyethoxy)acetic acid, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-(2-methoxyethoxy)propionic acid, Carboxylic acids such as 3-(2-ethoxyethoxy)propionic acid, 3-(2-propoxyethoxy)propionic acid, 3-(3-methoxypropoxy)propionic acid, 3-(3-ethoxypropoxy)propionic acid, 3-(3-propoxypropoxy)propionic acid, oleic acid, linoleic acid, sorbic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, lactic acid, salicylic acid, and trifluoroacetic acid are more preferred; formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, and 2-ethylhexanoic acid are particularly preferred; and acetic acid and 2-ethylhexanoic acid are particularly preferred.

[0265] The dicarbonyl compound (7) can be used directly in the form of an aqueous solution or an alcohol solution such as methanol or butanol.

[0266] The amount of the amine compound (8x) and the amine compound (8y) (hereinafter, the amine compound (8x) and the amine compound (8y) are collectively referred to as the amine compound (8)) used is usually 0.1 to 10 mol, preferably 0.5 to 3 mol, per 1 mol of the dicarbonyl compound (7). 2 mol of the amine compound (8) react with respect to 1 mol of the dicarbonyl compound (7) to form 1 mol of the imidazolium carboxylate (5). However, when the amount of the amine compound (8) is less than 2 mol, a polymer of the dicarbonyl compound (7) (raw material) and the dicarbonyl compound (7) is present in addition to the target imidazolium carboxylate (5). In addition, when more than 2 mol of the amine compound (8) is used per 1 mol of the dicarbonyl compound (7), an excess of the amine compound (8) is present in addition to the target imidazolium carboxylate (8). Even when the imidazolium carboxylate (5) is used in the presence of a compound other than the imidazolium carboxylate, an amide compound (2) can be obtained.

[0267] The ratio of the amine compound (8x) to the amine compound (8y) is not particularly limited, but is in the range of amine compound (8x):amine compound (8y) = 0:100 to 100:0. In the case where the ratio of amine compound (8x):amine compound (8y) = 0:100 or amine compound (8x):amine compound (8y) = 100:0, CR 4 R 5 R 6 The group shown = CR 9 R 10 R 11In addition, in CR 4 R 5 R 6 The group shown = CR 9 R 10 R 11 In cases other than the groups shown, that is, when the ratio of amine compound (8x):amine compound (8y) is not 0:100 or 100:0, the compound represented by formula (5) can be a mixture of compounds represented by the following formulas (5-1), (5-2), and (5-3).

[0268] [Chemical formula 30]

[0269]

[0270] (In formula (5-1), formula (5-2) and formula (5-3), R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 and R 14 Each is as defined above. 4 R 5 R 6 The groups and CR shown 9 R 10 R 11 The group shown may be adamantyl.)

[0271] The ratio of the compound represented by formula (5-1), the compound represented by formula (5-2), and the compound represented by formula (5-3) in the mixture varies depending on the ratio of the amine compound (8x) and the amine compound (8y) used in the reaction. The compound represented by formula (5-1), the compound represented by formula (5-2), and the compound represented by formula (5-3) are all contained in the imidazolium carboxylate (5).

[0272] Formaldehyde can be used directly 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 (9).

[0273] The amount of the carboxylic acid (9) used is usually 0.1 to 10 mol, preferably 0.5 to 2 mol, and more preferably 1 to 1.5 mol, based on 1 mol of the dicarbonyl compound (7).

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

[0275] The solvent may be used or not. When a solvent is used, the solvent used is not particularly limited as long as it does not affect the reaction. As a specific example of the solvent, 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, 1,2-dichloroethane, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, lower alcohols such as methanol and ethanol, N,N-dimethylformamide, acetonitrile, water, etc. are preferably aromatic hydrocarbons, lower alcohols, water, and particularly preferably toluene and water. The solvent may also be mixed and used in combination of two or more as needed.

[0276] The amount of the solvent used is usually 50 parts by mass or less, preferably 0.1 to 10 parts by mass, based on 1 part by mass of the dicarbonyl compound (7).

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

[0278] After the reaction is completed, the imidazolium carboxylate (5) can be isolated by removing impurities (eg, unreacted raw materials) by washing with an organic solvent or concentrating the reaction solution. It can also be purified by recrystallization or the like as needed.

[0279] Carbonate (6) will be described.

[0280] In formula (6), R 15 and R 16 are the same or different and represent a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a methyl group. 15 and R 16 They can form a ring structure together with the oxygen atom to which they are bonded. Examples of hydrocarbon groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, and phenyl. Specific examples of carbonates include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, and dihexyl carbonate, and alkylene carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate. Preferred examples include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate, and particularly preferred is dimethyl carbonate.

[0281] The amount of the carbonate (6) used is usually 1 mole or more, preferably 1 to 6 moles, per 1 mole of the imidazolium carboxylate (5). Furthermore, when the imidazolium carboxylate (5) contains excess carboxylic acid and water, these react with the carbonate (6). Therefore, the carbonate (6) is usually used in an excess amount of 1 mole or more, preferably 1 to 6 moles, per 1 mole of the total excess carboxylic acid and water in the imidazolium carboxylate (5).

[0282] In reaction 1, a solvent may be used or not. When a solvent is used, the solvent used is not particularly limited as long as it does not affect the reaction. Specific examples of solvents include monohydric alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol, 1-methoxy-2-propanol, and ethoxyethanol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, and diethylene glycol; glycol monoalkyl ether solvents such as dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene, benzene, and xylene; aliphatic hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane, and octane; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and 4-methyl-2-pentanone, etc., preferably a monohydric alcohol solvent, particularly preferably methanol. The amount of solvent used is generally 50 parts by mass or less, preferably 10 parts by mass or less, relative to 1 part by mass of imidazolium carboxylate (5).

[0283] In Reaction 1, the optimal reaction temperature varies depending on the raw materials, solvent, etc., but is generally room temperature or higher, preferably 20 to 200° C. In this specification, room temperature refers to approximately 20° C. The reaction time is generally 0.1 to 48 hours, preferably 1 to 24 hours.

[0284] In Reaction 1, the reaction may be carried out under an inert gas atmosphere such as nitrogen, argon, or helium that does not affect the reaction, if necessary.

[0285] After the reaction is completed, the reaction solution can be concentrated to remove the solvent as needed. In addition, if carbonate (6) or solvent remains in the reaction solution, the reaction solution can be concentrated to remove carbonate (6) or solvent.

[0286] Reaction 2 will be described.

[0287] The reaction product obtained in Reaction 1 (hereinafter sometimes referred to as reaction product (R)) is reacted with an isocyanate compound represented by formula (10) to produce an amide compound (2).

[0288] The isocyanate compound represented by formula (10) (hereinafter referred to as isocyanate compound (10)) will be described.

[0289] [Chemical Formula 31]

[0290]

[0291] (In formula (10), B and y are each as defined above.)

[0292] In the present invention, the isocyanate compound (10) is preferably a compound represented by the following formula (10-1), (10-2) or (10-3).

[0293] Formula (10-1):

[0294] [Chemical Formula 32]

[0295] R 12 -NCO (10-1)

[0296] (In formula (10-1), R 12 As defined above.)

[0297] Formula (10-2):

[0298] [Chemical Formula 33]

[0299] OCN-R 13 -NCO (10-2)

[0300] (In formula (10-2), R 13 As defined above.)

[0301] Formula (10-3):

[0302] [Chemical Formula 34]

[0303]

[0304] (In formula (10-3), E 1 、E 2 、E 3 , a, b, c, d, e, f, g are each as defined above.)

[0305] In the present invention, as the isocyanate compound (10), a polymer such as polymethylene polyphenyl polyisocyanate (polymeric MDI) may be used.

[0306] Specific examples of the isocyanate compound (10) are shown below. However, the present invention is not limited to these. In the following specific examples, Me represents a methyl group, iPr represents an isopropyl group, Bu represents an n-butyl group, Oct represents an n-octyl group, and MeO represents a methoxy group.

[0307] [Chemical Formula 35]

[0308]

[0309] [Chemical Formula 36]

[0310]

[0311] [Chemical Formula 37]

[0312]

[0313] [Chemical Formula 38]

[0314]

[0315] (Where n is as defined above.)

[0316] The isocyanate compound (10) is preferably a compound represented by the formula (10-1-5), (10-1-19), (10-2-3), or (10-3-1), and more preferably a compound represented by the formula (10-1-19) or (10-3-1).

[0317] The isocyanate compound (10) may be used alone or as a mixture of two or more.

[0318] In Reaction 2, the isocyanate compound (10) is usually used in an amount such that the isocyanate group in the isocyanate compound (10) is 0.8 mol or more, preferably 1 to 3 mol, per 1 mol of the imidazolium carboxylate (5).

[0319] The reaction temperature is not particularly limited, but is usually -10°C or higher, preferably 0 to 200°C, and more preferably 20 to 150°C. The reaction time is usually 0.1 to 48 hours, preferably 0.5 to 24 hours.

[0320] When a solvent is used, as a solvent, for example, aromatic hydrocarbon solvents such as toluene, benzene, and xylene can be cited; aliphatic hydrocarbon solvents such as methylcyclohexane, cyclohexane, hexane, heptane, and octane; halogenated hydrocarbon solvents such as butyl chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and 4-methyl-2-pentanone, etc., preferably aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, ester solvents, ketone solvents, particularly preferably toluene, xylene, chlorobenzene, butyl acetate, 4-methyl-2-pentanone. Solvents can also be mixed and used in two or more kinds as needed. In addition, when the reaction product (R) contains the solvent used in reaction 1, the solvent can also be used as a solvent in reaction 2, or the above-mentioned solvent can be further added. In this case, a solvent different from reaction 1 can be used.

[0321] The amount of the solvent used is usually 50 parts by mass or less, preferably 0.1 parts by mass or more and 35 parts by mass or less, relative to 1 part by mass of the imidazolium carboxylate (5).

[0322] If necessary, the reaction may be carried out under an inert gas atmosphere such as nitrogen, argon, or helium that does not affect the reaction.

[0323] After the reaction is completed, the solvent can be removed by concentrating or filtering the reaction solution to obtain the amidated compound (2). If necessary, the amidated compound (2) can be purified by recrystallization or column separation.

[0324] In the present invention, the amidate compound (2) preferably functions as a blocking agent dissociation catalyst for blocked polyisocyanates. For example, when used as a blocking agent dissociation catalyst for blocked polyisocyanate compounds blocked with oxime compounds such as methyl ethyl ketone oxime, the oxime such as methyl ethyl ketone oxime is dissociated to form a polyisocyanate, which further promotes the reaction with the compound having an isocyanate-reactive group described later.

[0325] In the blocked polyisocyanate composition of the present invention, the mixing ratio of the blocked polyisocyanate compound to the amidate compound (2) is determined according to the desired physical properties and is not particularly limited. It is generally in the range of amide groups (mol) of the amidate compound (2) / [effective isocyanate groups (mol) of the blocked polyisocyanate compound] = 0.001 to 0.5, preferably 0.01 to 0.1. It should be noted that the amide groups of the amide compound (2) are functional groups represented by the following formula (A), and the effective isocyanate groups of the blocked polyisocyanate compound are isocyanate groups regenerated when the blocking agent dissociates from the blocked polyisocyanate compound.

[0326] Formula (A):

[0327] [Chemical Formula 39]

[0328]

[0329] (In formula (A), R 4 ~R 11 Each is as defined above. 4 R 5 R 6 or CR 9 R 10 R 11 It may be an adamantyl group.)

[0330] The blocked polyisocyanate composition of the present invention may contain, as necessary, known polyurethane production catalysts, additives, pigments, solvents, and the like that are commonly used in the art.

[0331] Known catalysts for polyurethane production are not particularly limited, and examples thereof include tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanoate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octoate, and tin laurate; bismuth compounds such as bismuth octoate, bismuth naphthenate, and bismuth acetylacetonate; tetra-n-butyl titanate, tetraisopropyl titanate; Ester, titanium terephthalate and other titanium compounds; 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, Tertiary amine compounds such as 4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salts; and quaternary ammonium salts such as tetraalkylammonium organic acid salts such as tetramethylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

[0332] 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 anti-coloring agents, hindered phenol-based, phosphorus-based, sulfur-based, hydrazide-based and other antioxidants, tin-based, zinc-based, amine-based and other urethanization catalysts, leveling agents, rheology control agents, pigment dispersants, and the like.

[0333] 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, and pigments such as carbon pigments, metallic foil pigments, and rust-proof pigments.

[0334] The solvent is not particularly limited, and examples thereof include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; polyols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerol; and water. These solvents may be used alone or in combination of two or more.

[0335] The thermosetting resin composition of the present invention will be described.

[0336] The thermosetting resin composition of the present invention comprises the blocked polyisocyanate composition of the present invention and a compound having an isocyanate-reactive group.

[0337] Examples of the compound having an isocyanate-reactive group include compounds having two or more active hydrogen groups, such as polyols, polyamines, and alkanolamines. These compounds having an isocyanate-reactive group may be a mixture of two or more.

[0338] In the present invention, a polyol is a compound having two or more hydroxyl groups. Examples thereof include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and fluoropolyols. Among these, acrylic polyols are preferred from the perspectives of weather resistance, chemical resistance, and hardness. Alternatively, polyester polyols are preferred from the perspectives of mechanical strength and oil resistance. These polyols may be a mixture of two or more.

[0339] Examples of the polyether polyol include active hydrogen compounds such as aliphatic amine polyols, aromatic amine polyols, Mannich polyols, polyols, polyphenols, and bisphenols, and compounds obtained by adding alkylene oxides thereto. These polyether polyols may be a mixture of two or more.

[0340] Examples of aliphatic amine polyols include alkylenediamine polyols and alkanolamine polyols. These polyol compounds are polyfunctional polyol compounds with terminal hydroxyl groups, formed by ring-opening addition of at least one cyclic ether such as ethylene oxide or propylene oxide using an alkylenediamine or alkanolamine as an initiator. Known alkylenediamines can be used without limitation. Specifically, alkylenediamines having 2 to 8 carbon atoms, such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, and neopentyldiamine, are preferably used. These aliphatic amine polyols may be a mixture of two or more.

[0341] Aromatic amine polyols are multifunctional polyether polyol compounds having terminal hydroxyl groups formed by ring-opening addition of at least one of cyclic ethers such as ethylene oxide and propylene oxide using aromatic diamines as initiators. As initiators, known aromatic diamines can be used without limitation. Specifically, 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, etc. can be mentioned. Among them, toluenediamine (2,4-toluenediamine, 2,6-toluenediamine or a mixture thereof) is particularly preferably used. These aromatic amine polyols can be a mixture of two or more.

[0342] Mannich polyols are active hydrogen compounds obtained by the Mannich reaction of phenol and / or its alkyl-substituted derivatives, formaldehyde, and alkanolamines, or polyol compounds obtained by ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide to such compounds. These Mannich polyols may be mixtures of two or more.

[0343] Examples of the polyol include dihydric alcohols (e.g., ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and neopentyl glycol), and trivalent or higher-valent alcohols (e.g., glycerol, trimethylolpropane, pentaerythritol, methyl glucoside, sorbitol, and sucrose). These polyols may be a mixture of two or more.

[0344] Examples of the polyphenol include pyrogallol and hydroquinone. These polyphenols may be a mixture of two or more.

[0345] Examples of the bisphenols include bisphenol A, bisphenol S, bisphenol F, and low condensation products of phenol and formaldehyde. These bisphenols may be a mixture of two or more.

[0346] The polyester polyol can be obtained, for example, by subjecting a dibasic acid alone or in a mixture of two or more thereof to a condensation reaction with a polyol alone or in a mixture of two or more thereof.

[0347] Examples of the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.

[0348] Examples of the polyol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, and ethoxylated trimethylolpropane.

[0349] A specific method for producing polyester polyols is, for example, mixing the above components and heating at about 160 to 220° C. to perform a condensation reaction. Alternatively, polycaprolactones obtained by ring-opening polymerization of lactones such as ε-caprolactone using a polyol can also be used as polyester polyols.

[0350] These polyester polyols can be modified using aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates derived therefrom, etc. Among them, from the viewpoints of weather resistance and yellowing resistance, polyester polyols are preferably modified using aliphatic diisocyanates, alicyclic diisocyanates, and polyisocyanates derived therefrom.

[0351] When the thermosetting resin composition of the present embodiment is used as a water-based base coating, the polyester polyol can be made water-soluble or water-dispersible by preliminarily neutralizing a portion of the carboxylic acid derived from a dibasic acid or the like in the polyester polyol with a base such as amine or ammonia.

[0352] The polyether polyol can be obtained, for example, by any one of the following methods (1) to (3).

[0353] (1) A method of obtaining polyether polyols by randomly or block-adding an alkylene oxide alone or in a mixture to a polyvalent hydroxy compound alone or in a mixture using a catalyst.

[0354] Examples of the catalyst include hydroxides (lithium, sodium, potassium, etc.), strong basic catalysts (alkoxides, alkylamines, etc.), and composite metal cyanide complexes (metalloporphyrins, zinc hexacyanocobaltate complexes, etc.).

[0355] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide.

[0356] (2) A method of obtaining polyether polyols by reacting an alkylene oxide with a polyamine compound.

[0357] Examples of the polyamine compound include ethylenediamines.

[0358] Examples of the alkylene oxide include the same alkylene oxides as exemplified in (1).

[0359] (3) A method of obtaining so-called polymer polyols by polymerizing acrylamide or the like using the polyether polyols obtained in (1) or (2) as a medium.

[0360] Examples of the polyvalent hydroxy compound include the following polyvalent hydroxy compounds (i) to (vi).

[0361] (i) Diglycerol, bis(trimethylol)propane, pentaerythritol, dipentaerythritol, etc.

[0362] (ii) Sugar alcohol compounds such as erythritol, D-threitol, L-arabitol, ribitol, xylitol, sorbitol, mannitol, galactitol, and rhamnitol.

[0363] (iii) Monosaccharides such as arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and deoxyribose.

[0364] (iv) Disaccharides such as trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and melibiose.

[0365] (v) trisaccharides such as raffinose, gentiotriose, and melezitose.

[0366] (vi) Tetrasaccharides such as stachyose.

[0367] The acrylic polyol can be obtained, for example, by polymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule, or by copolymerizing a polymerizable monomer having one or more active hydrogen atoms in one molecule and, if necessary, other monomers copolymerizable with the polymerizable monomer.

[0368] Examples of the polymerizable monomer having one or more active hydrogen atoms in one molecule include the following polymerizable monomers (i) to (vi), which may be used alone or in combination of two or more.

[0369] (i) Acrylates having active hydrogen, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate.

[0370] (ii) Methacrylic acid esters having active hydrogen, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

[0371] (iii) (meth)acrylates having polyvalent active hydrogen, such as (meth)acrylate monoesters of triols such as glycerol and trimethylolpropane.

[0372] (iv) Monoethers of polyether polyols (eg, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.) and the above-mentioned (meth)acrylates having active hydrogen.

[0373] (v) Adducts of glycidyl (meth)acrylate and monobasic acids (such as acetic acid, propionic acid, p-tert-butylbenzoic acid, etc.).

[0374] (vi) Adducts obtained by ring-opening polymerization of lactones (eg, ε-caprolactam, γ-valerolactone, etc.) with the active hydrogen of the above-mentioned (meth)acrylic acid esters having active hydrogen.

[0375] Examples of other monomers copolymerizable with the polymerizable monomers include the following monomers (i) to (iv), which may be used alone or in combination of two or more.

[0376] (i) (Meth)acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, and glycidyl methacrylate.

[0377] (ii) Unsaturated amides such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid (unsaturated carboxylic acids such as acrylamide, N-methylol acrylamide, and diacetone acrylamide).

[0378] (iii) Vinyl monomers having a hydrolyzable silyl group, such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane.

[0379] (iv) Other polymerizable monomers such as styrene, vinyltoluene, vinyl acetate, acrylonitrile, and dibutyl fumarate.

[0380] Specific examples of the production method of acrylic polyols include a method of obtaining acrylic polyols by solution polymerization of the above-mentioned monomer components in the presence of a known radical polymerization initiator such as a peroxide or an azo compound, and then diluting the mixture with an organic solvent as needed.

[0381] When the thermosetting resin composition of this embodiment is used as a water-based base coating, a water-based acrylic polyol can be produced by using a known method such as solution polymerization of the monomer components to convert them into an aqueous layer or emulsion polymerization. In this case, the acidic portion of a carboxylic acid-containing monomer such as acrylic acid or methacrylic acid, or a sulfonic acid-containing monomer, can be neutralized with an amine or ammonia to impart water solubility or water dispersibility to the acrylic polyol.

[0382] Examples of the polyolefin polyol include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene having two or more hydroxyl groups, and hydrogenated polyisoprene having two or more hydroxyl groups.

[0383] In addition, in the polyolefin polyol, the number of hydroxyl groups is preferably 3 from the viewpoint of obtaining higher coating film strength.

[0384] In this specification, "fluoropolyol" refers to a polyol containing fluorine in its molecule. Specific examples of the fluoropolyol include copolymers of fluoroolefins, cyclovinyl ethers, hydroxyalkyl vinyl ethers, and vinyl monocarboxylates disclosed in Japanese Patent Application Laid-Open Nos. 57-34107 and 61-275311.

[0385] The lower limit of the hydroxyl value of the polyol is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and even more preferably 30 mgKOH / g or more.

[0386] On the other hand, the upper limit of the hydroxyl value of the polyol is not particularly limited, but may be, for example, 200 mgKOH / g or less.

[0387] That is, the hydroxyl value of the polyol is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 20 mgKOH / g to 200 mgKOH / g, and even more preferably 30 mgKOH / g to 200 mgKOH / g.

[0388] Furthermore, the acid value of the polyol is preferably 0 mgKOH / g or more and 30 mgKOH / g or less.

[0389] The hydroxyl value and the acid value can be measured in accordance with JIS K1557.

[0390] The molar equivalent ratio (NCO / OH) of the isocyanate groups in the blocked polyisocyanate composition to the hydroxyl groups in the polyol is preferably 0.2 to 5.0, more preferably 0.4 to 3.0, and even more preferably 0.5 to 2.0.

[0391] As the polyamine, a polyamine having two or more primary or secondary amino groups in one molecule is used, and among them, a polyamine having three or more primary or secondary amino groups in one molecule is preferred.

[0392] Specific examples of the polyamine include diamines such as ethylenediamine, propylenediamine, butylenediamine, triethylenediamine, hexamethylenediamine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, and isophoronediamine; chain polyamines having three or more amino groups such as bis-hexamethylenetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, and tetrapropylenepentamine; and cyclic polyamines such as 1,4,7,10,13,16-hexaazacyclooctadecane, 1,4,7,10-tetraazacyclodecane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,8,11-tetraazacyclotetradecane.

[0393] The alkanolamine is a compound having an amino group and a hydroxyl group in one molecule. Examples of the alkanolamine include monoethanolamine, diethanolamine, aminoethylethanolamine, N-(2-hydroxypropyl)ethylenediamine, mono-, di-(n- or iso-)propanolamine, ethylene glycol-bis-propylamine, neopentanolamine, and methylethanolamine.

[0394] The thermosetting resin composition of the present embodiment may contain a melamine-based curing agent such as a fully alkyl type, a methylol type, or an alkylamino type alkyl type, as needed.

[0395] The thermosetting resin composition of the present embodiment may contain an organic solvent.

[0396] Furthermore, the compound having an isocyanate-reactive group and the blocked polyisocyanate composition may contain an organic solvent.

[0397] The organic solvent is preferably an organic solvent that is compatible with the blocked polyisocyanate composition.

[0398] Specific examples of the organic solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; alcohols such as methanol, ethanol, 2-propanol, butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-butoxyethanol; polyols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, and glycerol; and water. These solvents may be used alone or in combination of two or more.

[0399] In addition, the thermosetting resin composition of this embodiment can be used in the form of an aqueous thermosetting resin composition dissolved or dispersed in water. When the thermosetting resin composition of the present invention is used as an aqueous thermosetting resin composition, in order to improve the compatibility of the thermosetting resin composition, a solvent that exhibits a tendency to miscibility with surfactants and water can also be used for the blocked polyisocyanate composition of the present invention. Examples of surfactants include anionic surfactants such as fatty soaps, rosin acid soaps, alkyl sulfonates, dialkylaryl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, and polyoxyethylene alkylaryl sulfates; and nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, and polyoxyethylene polyoxypropylene block copolymers. Examples of the solvent that tends to be miscible with water include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutyl alcohol, butylene glycol, N-methylpyrrolidone, butyl diglycol, and butyl diglycol acetate.

[0400] Among the above-mentioned solvents, preferred are diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, isobutyl alcohol, butylene glycol, N-Methyl pyrrolidone, butyl diglycol, more preferably diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether. These solvents can be used alone or in combination of two or more. In addition, the solvents of esters such as ethyl acetate, n-butyl acetate, and acetic acid cellosolve sometimes hydrolyze the solvent itself during storage, so they are not preferred.

[0401] In the thermosetting resin composition of the present invention, the mixing ratio of the blocked polyisocyanate composition to the compound having an isocyanate-reactive group is determined according to the desired physical properties and is not particularly limited. The mixing ratio is generally in the range of [the amount (mol) of effective isocyanate groups of the blocked polyisocyanate compound in the blocked polyisocyanate composition] / [the amount (mol) of active hydrogen groups of the compound having an isocyanate-reactive group] = 0.2 to 5, preferably in the range of 0.5 to 3. It should be noted that the effective isocyanate groups of the blocked polyisocyanate compound refer to the isocyanate groups regenerated when the blocking agent dissociates from the blocked polyisocyanate compound.

[0402] The thermosetting resin composition of the present invention may contain, as needed, known polyurethane production catalysts, additives, pigments, and the like commonly used in the art, and may also be mixed with known blocked polyisocyanates.

[0403] Known catalysts for polyurethane production are not particularly limited, and examples thereof include tin compounds such as dibutyltin dilaurate, dibutyltin di-2-ethylhexanoate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin dioxide, dioctyltin dioxide, tin acetylacetonate, tin acetate, tin octoate, and tin laurate; bismuth compounds such as bismuth octoate, bismuth naphthenate, and bismuth acetylacetonate; tetra-n-butyl titanate, tetraisopropyl titanate; Ester, titanium terephthalate and other titanium compounds; 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, tertiary ammonium compounds such as 4-diazabicyclo[2.2.2]octane (DABCO), 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole; tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salts; tetraalkylammonium organic acid salts such as tetramethylammonium-2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium-2-ethylhexanoate.

[0404] 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 anti-coloring agents, hindered phenol-based, phosphorus-based, sulfur-based, hydrazide-based and other antioxidants, tin-based, zinc-based, amine-based and other urethanization catalysts, leveling agents, defoaming agents, rheology control agents, thixotropy-imparting agents and thickeners, light stabilizers, plasticizers, surfactants, coupling agents, flame retardants, rust inhibitors, fluorescent whitening agents, pigment dispersants and other various additives commonly used in this technical field.

[0405] 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, and pigments such as carbon pigments, metallic foil pigments, and rust-proof pigments.

[0406] Examples of known blocked polyisocyanates include blocked polyisocyanates obtained by reacting a polyisocyanate with a known blocking agent. Examples of known blocking agents include phenolic compounds such as phenol, thiophenol, methylthiophenol, xylenol, cresol, resorcinol, nitrophenol, and chlorophenol; oxime compounds such as acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; alcohol compounds such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, tert-amyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and benzyl alcohol; pyrazole compounds such as 3,5-dimethylpyrazole and 1,2-pyrazole; and 1,2-pyrazole. ,4-triazole and other triazole compounds; halogen-substituted alcohol compounds such as chloroethanol and 1,3-dichloro-2-propanol; lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; active methylene compound compounds such as methyl acetoacetate, ethyl acetoacetate, acetylacetone, methyl malonate, ethyl malonate, in addition to these, amine compounds, imide compounds, thiol compounds, imine compounds, urea compounds, diaryl compounds, etc. can also be mentioned.

[0407] The thermosetting resin composition of the present invention can be used in coatings 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 window frames, home appliances such as office equipment, etc., coating materials such as artificial leather and rubber rollers, inks, adhesives, pressure-sensitive adhesives, sealing materials for electronic components, sealing materials for automobiles and buildings, etc., molding materials for 3D printers, etc.

[0408] Next, the curing method of the thermosetting resin composition of the present invention will be described.

[0409] In the method of the present invention, the thermosetting resin composition, which is a mixture of the blocked polyisocyanate composition and the compound having an isocyanate-reactive group, is heated.

[0410] The reaction temperature varies depending on the fluoroalcohol-blocked polyisocyanate compound (BI) and the amidate compound (2) in the blocked polyisocyanate composition, but may be about 60 to 250° C., preferably about 80 to 200° C. The reaction time may be about 30 seconds to 5 hours, preferably about 1 minute to 60 minutes.

[0411] The cured product of the present invention can be produced by the above-mentioned method for curing the thermosetting resin composition of the present invention.

[0412] Example

[0413] The present invention will be described in more detail using Production Examples and Examples, but the present invention is not limited to these Examples.

[0414] (1) Infrared spectroscopic analysis conditions

[0415] Device: FT-IR-6600 manufactured by JASCO Corporation

[0416] Measurement method: Total reflection measurement method (crystal: germanium)

[0417] Cumulative number of times: 16 times

[0418] (2) 1 H-NMR analysis conditions

[0419] Device: AV400 manufactured by Bruker Co., Ltd.

[0420] Frequency: 400MHz

[0421] (3) Curing temperature and time measurement conditions

[0422] Device: MADOKA, an automatic curing time measuring device manufactured by Cyber ​​Co., Ltd.

[0423] Stirring rod: Model 3JC-5060W

[0424] Stirring speed: 100 rpm rotation, 25 rpm revolution

[0425] (4) Calculation method of solid content

[0426] About 1.5 g of a 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.

[0427] (5) Composition of thermosetting resin composition

[0428] The blocked polyisocyanate compound, the compound having an isocyanate-reactive group, and the amidate compound were added to achieve a ratio of available NCO groups (mol): hydroxyl groups (mol): amide groups (mol) = 1.00:0.95:0.05. Methyl isobutyl ketone was added to achieve a ratio of solid content of the blocked polyisocyanate compound (g): solvent (g) = 1.0:1.0. Note that the solvent used for dilution of the blocked polyisocyanate compound is included in this calculation. Available NCO groups (mol) and hydroxyl groups (mol) were calculated using the following formula.

[0429] Effective NCO group (mol) = Amount of blocked polyisocyanate added (g) ÷ Effective NCO group content of blocked polyisocyanate (%) ÷ 4.202

[0430] Hydroxyl (mol) = amount of polyol added (g) × hydroxyl value of polyol (mg KOH / g) ÷ 56.1

[0431] Preparation Example B-1 Synthesis of MEKO-terminated Biuret-type HDI

[0432] Into a nitrogen-purged 200 mL three-necked reactor, 60.0 g (NCO group: 0.33 mol) of biuret-type HDI (Desmodur N3200A, NCO group content: 22.8% by weight, manufactured by Sumika Covestro Urethane Co., Ltd.) and 36.9 g of methyl isobutyl ketone (hereinafter referred to as MIBK) were placed. The temperature was raised to 65°C, and 0.6 g of triethylamine (hereinafter referred to as TEA) was added. Then, 29.0 g (0.33 mol) of methyl ethyl ketone oxime (hereinafter referred to as MEKO) and 22.9 g of MIBK were added dropwise, and the mixture was stirred at 65°C for 2 hours. Infrared spectroscopic analysis confirmed that the isocyanate group had a concentration of 2270 cm -1 The infrared absorption peak near the 1% alkyl group (I) disappeared. The resulting reaction solution was concentrated under reduced pressure to remove TEA and most of the MIBK. 17.4 g of MIBK was then added to obtain 117.9 g of a MIBK solution of a MEKO-terminated biuret-type HDI. The resulting TFE-terminated biuret-type HDI had a solids content of 74.7% and an effective NCO group content of 11.6%.

[0433] Preparation Example A-1 Synthesis of DOIm_PI

[0434] [Chemical Formula 40]

[0435]

[0436] (Process 1)

[0437] 1049.9 g (8.12 mol) of n-octylamine was added to a 3L 4-mouth reactor after nitrogen substitution, and the temperature was raised to 80°C. Then, a mixture of 366.0 g (6.09 mol) of acetic acid and 290.4 g of 42 wt% formalin aqueous solution (pure formaldehyde content 4.06 mol) was added dropwise to the reactor over 1 hour. The solution after addition was stirred for 30 minutes and cooled to 40°C. 581.0 g of 41 wt% glyoxal aqueous solution (pure glyoxal content 4.06 mol) was added dropwise to the solution cooled to 40°C over 30 minutes and stirred for 5 hours. After stirring, the obtained reaction solution was concentrated under reduced pressure to obtain 1582.0 g of a reaction product containing 1,3-di-n-octylimidazolium acetate. Tetralin was added as an internal standard substance for 1 H-NMR analysis showed that the content of pure 1,3-di-n-octylimidazolium acetate was 1224.9 g (3.47 mol, yield 85.5%).

[0438] (Process 2)

[0439] A 5 L pressure vessel was charged with 1070.1 g (pure product content: 828.6 g, 2.35 mol) of the reaction product obtained in step 1, 1069.5 g of toluene, and 756.0 g (8.39 mol) of dimethyl carbonate, and the atmosphere was purged with nitrogen. The mixture was then stirred at 120°C for 15 hours. After stirring, the resulting reaction mixture was concentrated under reduced pressure to 1043.5 g, to which toluene was added to obtain 2058.6 g of a toluene solution.

[0440] (Process 3)

[0441] Into a 3L 4-mouth reactor after nitrogen substitution, 1700.2g of the toluene solution obtained in step 2 and 807.4g of toluene were added and heated to reflux. 229.7g (1.93mol) of phenyl isocyanate was added dropwise to the reaction solution after heating to reflux over 2 hours, and stirred for 10 hours. After stirring, the obtained reaction mixture was concentrated to 1433.1g, 761.0g of heptane was added, and heated to 50°C to dissolve all the solids to prepare a mixed solution. Then, the obtained mixed solution was cooled from 50°C to 30°C to precipitate crystals, stirred at 30°C for 1 hour, cooled to 10°C at a rate of 10°C per hour for 2 hours, and further stirred at 10°C for 1 hour to obtain a slurry liquid. The obtained slurry liquid was filtered to obtain 426.8g (1.04mol, 53.2% process yield from step 2) of the compound represented by the above formula (DOIm_PI) in the form of a slightly yellow solid. DOIm_PI 1 The results of H-NMR analysis are shown below.

[0442] 1 H-NMR (DMSO-d6) δ (ppm) = 9.32 (s, 1H), 7.80 (s, 2H), 4.17 (t, J = 9.6Hz, 4H), 1.78 (m, 4H), 1.63 (s, 3H), 1.23 (m, 20H), 0.85 (t, J = 6.4Hz, 6H)

[0443] Preparation Example A-2 Synthesis of DtBIm_PI

[0444] [Chemical Formula 41]

[0445]

[0446] (Process 1)

[0447] 100.0 g (1.36 mol) of tert-butylamine was added to a 300 mL 4-mouth reactor after nitrogen substitution and the temperature was raised to 40°C. Then, a mixture of 62.1 g (1.03 mol) of acetic acid and 50.8 g of a 40 wt% formalin aqueous solution (pure formaldehyde content 0.68 mol) was added dropwise to the reactor over 1 hour and stirred for 30 minutes. 99.0 g of a 40 wt% glyoxal aqueous solution (pure glyoxal content 0.68 mol) was added dropwise to the stirred solution over 30 minutes and stirred for 5 hours. After stirring, the obtained reaction solution was concentrated under reduced pressure, 100.0 g of H2O and 100.0 g of toluene were added, and a liquid separation operation was performed. The aqueous layer obtained after liquid separation was concentrated under reduced pressure to obtain 123.2 g of a reaction product containing 1,3-di-tert-butylimidazolium acetate.

[0448] (Process 2)

[0449] Into an 180 mL pressure vessel, 40.0 g of the reaction product containing 1,3-di-tert-butylimidazolium acetate obtained in step 1 and 52.6 g (0.58 mol) of dimethyl carbonate were added and nitrogen purged. The mixture was then stirred at 120°C for 6 hours. After stirring, the resulting reaction mixture was concentrated under reduced pressure to obtain a black solid. The resulting black solid was washed with 100.0 g of acetone to obtain 38.6 g of a white solid.

[0450] (Process 3)

[0451] 10.0 g of the white solid obtained in step 2 and 40.0 g of chlorobenzene were added to a 100 mL 3-necked reactor after nitrogen substitution, and the mixture was heated to reflux. After heating to reflux, a mixed solution of 5.9 g (0.043 mol) of phenyl isocyanate and 10.0 g of chlorobenzene was added dropwise to the reactor over 10 minutes and stirred for 1 hour. After stirring, the obtained reaction mixture was filtered and the filter residue was washed with 50.0 g of heptane to obtain 7.84 g (0.017 mmol, 30.0% yield from step 1) of a composition containing the compound represented by the above formula (Dt BIm_PI). DtBIm_PI 1 The results of H-NMR analysis are shown below.

[0452] 1 H-NMR (CDCl3) δ (ppm) = 7.56 (d, J = 6.6 Hz, 2H), 7.31 (t, J = 6.6 Hz, 2H), 7.07 (s, 2H) 6.93 (t, J = 7.2 Hz, 1H), 1.87 (s, 18H)

[0453] Preparation Example A-Synthesis of 3DtOIm_PI

[0454] [Chemical Formula 42]

[0455]

[0456] (Process 1)

[0457] To a nitrogen-purged, 100-ml, three-necked reactor were added 6.97 g (0.116 mol) of acetic acid, 5.80 g of a 40 wt% formalin aqueous solution (purified formaldehyde content: 0.077 mol), and 11.2 g of a 40 wt% glyoxal aqueous solution (purified glyoxal content: 0.077 mol). The mixture was heated to 50°C. Subsequently, 1.00 g (0.154 mol) of 1,1,3,3-tetramethylbutylamine was added dropwise over 2 hours to the mixture in the reactor, followed by stirring for 2 hours. After stirring, the resulting reaction solution was concentrated under reduced pressure to yield 24.8 g of a reaction product containing 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate.

[0458] (Process 2)

[0459] A 180 mL pressure vessel was charged with 24.8 g of the reaction product containing 1,3-bis(1,1,3,3-tetramethylbutyl)imidazolium acetate obtained in Step 1, 27.0 g (0.297 mol) of dimethyl carbonate, and 30.0 g of toluene, and the atmosphere was purged with nitrogen. The mixture in the pressure vessel was then stirred at 120°C for 6 hours. After stirring, the resulting reaction mixture was concentrated under reduced pressure to yield 20.0 g of a dark brown solid.

[0460] (Process 3)

[0461] 10.4 g of the dark brown solid obtained in step 2 and 40.0 g of chlorobenzene were added to a 100 mL 3-necked reactor after nitrogen substitution, and the mixture was heated to reflux. The mixed solution after heating to reflux was cooled to 60°C, and a mixed solution of 3.9 g (0.032 mol) of phenyl isocyanate and 12.2 g of chlorobenzene was added dropwise thereto over 10 minutes, and stirred at 60°C for 1 hour. After stirring, the obtained reaction mixture was cooled to room temperature, 50.0 g of heptane was added thereto, and the mixture was filtered. The filter residue was washed with 50.0 g of heptane to obtain 7.55 g (0.014 mmol, 36.0% yield from step 1) of a composition containing the compound represented by the above formula (Dt OIm_PI). DtOIm_PI 1 The results of H-NMR analysis are shown below.

[0462] 1H-NMR (CDCl3) δ (ppm) = 7.59 (d, J = 9.2Hz, 2H), 7.30 (t, J = 7.6Hz, 2H), 7.08 (s, 2H), 6.93 (t, J = 7.2Hz, 1H), 2.40 (m, 4H), 1.87 (m, 12H), 0.99 (s, 18H)

[0463] Preparation Example A-4 Synthesis of DtOIm_crMDI

[0464] [Chemical Formula 43]

[0465]

[0466] Into a nitrogen-purged 100 mL 3-necked reactor, 5.0 g of the dark brown solid obtained in step 2 of Production Example A-3 and 20.0 g of chlorobenzene were added and heated to reflux. After heating to reflux, a mixed solution of 1.52 g (0.012 mol of NCO group) of polymerized MDI (Sumidur44V20: solid content 100%, NCO group content 32.0%, manufactured by Sumika Covestro Urethane Co., Ltd.) and 5.0 g of chlorobenzene was added dropwise to the reactor over 10 minutes and stirred for 1 hour. After stirring, the obtained reaction mixture was added dropwise to 50.0 g of heptane and filtered, and the filter residue was washed with 50.0 g of heptane to obtain 4.28 g (0.014 mmol, 52.0% yield from step 1) of a composition of the compound represented by the above formula (DtOIm_crMDI). DtOctIm_crMDI 1 The results of H-NMR analysis are shown below.

[0467] 1 H-NMR (CDCl3) δ (ppm) = 7.52-7.48 (m), 7.35-7.30 (m), 7.13-7.11 (m), 7.04-7.00 (m), 1.87 (m), 1.32 (m), 0.93 (m)

[0468] Preparation Example A-5 Synthesis of OMIm_PI

[0469] [Chemical Formula 44]

[0470]

[0471] (Process 1)

[0472] Into a 180 mL autoclave purged with nitrogen, 25.0 g (139 mmol) of 1-octylimidazole, 16.7 g (185 mmol) of dimethyl carbonate and 25.1 g of methanol were added and stirred at 125° C. for 29 hours. After stirring, the reaction mixture was cooled to room temperature. 8.5 g (94 mmol) of dimethyl carbonate was added to the cooled reaction mixture and stirred at 130° C. for further 3 hours. The resulting reaction mixture was cooled to 25° C. to obtain 44.0 g of a methanol solution of 1-octyl-3-methylimidazolium-2-carboxylate (hereinafter abbreviated as OMIm-CO 2 ) (pure product content 33.0 g, 139 mmol, yield 99%).

[0473] (Process 2)

[0474] Into a 200 mL test tube purged with nitrogen, 4.0 g (pure content 13 mmol) of the methanol solution of OMIm-CO2 obtained in step 2, 1.5 g (13 mmol) of phenyl isocyanate, and 100 mL of toluene were added, and the resulting mixture was stirred at an internal temperature of 110°C for 3 hours. Concentrated under reduced pressure to obtain 3.3 g of the compound represented by the above formula (OMIm-PI). Furthermore, recrystallization was performed with butyl acetate to obtain high-purity OMIm-PI. The following shows the structure of the compound represented by the above formula. 1 H-NMR analysis results.

[0475] 1 H-NMR (CD3OD) δ (ppm) = 7.51 (s, 1H), 7.45, 7.33 (m, 6H), 4.37 (t, J = 7.4Hz, 2H ), 3.97(s,3H), 1.91-1.86(m,2H), 1.35-1.27(m,10H), 0.88(t,J=6.8Hz,3H)

[0476] Example 1

[0477] The MEKO-terminated biuret-type HDI obtained in Production Example B-1, polyester polyol (P-510, manufactured by Kuraray Co., Ltd.), and DtBIm-PI obtained in Production Example A-1 were added so that the composition of the thermosetting resin composition would be effective NCO groups (mol): hydroxyl groups (mol): amide groups (mol) = 1.00:0.95:0.05. Furthermore, MIBK was added so that the amount of solvent relative to the blocked polyisocyanate compound was 1.0 times by weight, and the mixture was stirred for 30 minutes to prepare a thermosetting resin composition.

[0478] Approximately 0.6 mL of the prepared thermosetting resin composition was poured onto the hot plate of an automatic curing time measuring device preheated to a predetermined temperature and stirred. The curing time was defined as the time from when the stirring torque fell below 1% (0.04 mN·m) immediately after the start of stirring to when the stirring torque exceeded 20% (0.86 mN·m). The curing time was measured at various temperatures from 150°C to 80°C, and the lowest temperature at which the composition cured within 30 minutes was determined. The results are shown in Table 1.

[0479] Examples 2, 3, and Comparative Examples 1 to 3

[0480] In Example 1, a thermosetting resin composition was prepared in the same manner as in Example 1, except that the end-capping agent dissociation catalyst was replaced with the one shown in Table 1. The curing time at various temperatures was measured, and the minimum temperature at which curing occurred within 30 minutes was determined. The results are shown in Table 1.

[0481] [Table 1]

[0482]

[0483] Minimum temperature for curing within 30 minutes

[0484] S: 85°C or less, A: 95°C or less, B: 100°C or less, C: over 100°C.

Claims

1. A blocked polyisocyanate composition comprising a blocked polyisocyanate compound and at least one amidate compound represented by the following formula (2). Formula (2): ， In formula (2), B represents a substituted or unsubstituted hydrocarbon group; R 4 、R 5 、R 6 、R 9 、R 10 and R 11 are the same or different, representing a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a heteroatom or not; R 7 and R 8 are the same or different and represent a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a heteroatom or not; R 4 and R 5 、R 5 and R 6 、R 7 and R 8 、R 9 and R 10 , or R 10 and R 11 Together with the carbon atoms to which they are bonded, they form a ring structure or do not form a ring structure; y is an integer from 1 to 20; CR 4 R 5 R 6 The group or CR shown 9 R 10 R 11 The groups shown are either adamantyl or not.

2. The blocked polyisocyanate composition according to claim 1, wherein B is a substituted or unsubstituted aromatic hydrocarbon group.

3. The blocked polyisocyanate composition according to claim 1 or 2, wherein R 4 、R 5 、R 9 and R 10 The same or different groups are hydrocarbon groups having 1 to 6 carbon atoms which may be substituted by a heteroatom or not.

4. The blocked polyisocyanate composition according to claim 1 or 2, wherein R 6 and R 11 The same or different hydrocarbon groups have 1 to 12 carbon atoms and are substituted or not substituted by heteroatoms.

5. The blocked polyisocyanate composition according to claim 1 or 2, wherein R 7 and R 8 A hydrogen atom.

6. The blocked polyisocyanate composition according to claim 1, wherein The amidate compound represented by formula (2) is any one of the five compounds represented by the following formulae: ， In the formula, n is 0 or an integer of 1 to 4.

7. The blocked polyisocyanate composition according to claim 1 or 2, wherein The blocked polyisocyanate compound is a reaction product of a blocking agent and polyisocyanate, and the blocking agent is an oxime-based blocking agent.

8. The blocked polyisocyanate composition according to claim 1 or 2, wherein The blocked polyisocyanate compound is a reaction product of a blocking agent and polyisocyanate, and the blocking agent is methyl ethyl ketone oxime. 9 . A thermosetting resin composition comprising the blocked polyisocyanate composition according to claim 1 and a compound having an isocyanate-reactive group.

10. The thermosetting resin composition according to claim 9, wherein The compound having an isocyanate-reactive group is a polyol compound. 11 . A method for producing a cured product, comprising the step of heating and curing the thermosetting resin composition according to claim 9 .

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