Amide imide compound, amine imide composition, curing agent, epoxy resin composition, method for producing amine imide compound, sealing material, and adhesive

Abstract

Provided are an amine imide compound, an amine imide composition, a curing agent, an epoxy resin composition, a method for producing an amine imide compound, a sealing material, and an adhesive which have excellent permeability and excellent curability and storage stability. An amine imide compound represented by formula (1), (2) or (3). (In formulae (1) to (3), each R1 independently represents a hydrogen atom, or a C1-15 monovalent organic group or n-valent organic group optionally having a hydroxyl group, a carbonyl group, an ester bond or an ether bond; r2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1-12 carbon atoms, or a heterocyclic ring having 7 or less carbon atoms formed by connecting R2 and R3; each R4 independently represents a hydrogen atom, or a monovalent organic group or an n-valent organic group optionally containing an oxygen atom and having 1-30 carbon atoms; and n represents an integer of 1-3. )

Description

[0001] This application is a divisional application of the application with the application date of July 14, 2021, application number 202180049228.8, and invention name of amine imide compound, amine imide composition, curing agent, epoxy resin composition, method for manufacturing amine imide compound, sealing material and adhesive. Technical Field

[0002] The present invention relates to an amine imide compound, an amine imide composition, a curing agent, an epoxy resin composition, a method for producing the amine imide compound, a sealing material and an adhesive. Background Art

[0003] Epoxy resins have long been used in a wide range of applications, including coatings, electrical and electronic insulation materials, and adhesives, due to the excellent mechanical, electrical, thermal, chemical resistance, and adhesive properties of their cured products.

[0004] The epoxy resin composition commonly used today is a so-called two-component epoxy resin composition in which two liquids, an epoxy resin and a curing agent, are mixed before use.

[0005] Two-component epoxy resin compositions can cure at room temperature. However, the epoxy resin and curing agent must be stored separately and measured and mixed according to the usage. This makes storage and handling relatively complicated. Furthermore, the usable time is limited, so large quantities cannot be mixed in advance.

[0006] To solve the above-mentioned problems of two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed (see, for example, Patent Documents 1 to 3). Examples of the one-component epoxy resin compositions include epoxy resins containing latent curing agents.

[0007] Furthermore, demands for today's electronic devices extend across multiple dimensions, including miniaturization, enhanced functionality, lightweighting, increased functionality, and multifunctionality. For example, semiconductor chip mounting technology is also demanding further miniaturization, miniaturization, and increased density through finer pitches between electrode pads. Consequently, underfill adhesives used in gaps between chips and substrates are required to penetrate into increasingly narrow gaps.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent No. 6282515

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 2003-96061

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2000-229927 Summary of the Invention

[0013] Problems to be solved by the invention

[0014] Latent curing agents used in one-component epoxy resin compositions are required to have both good curability and storage stability after mixing with the epoxy resin. Furthermore, they are also required to have good permeability into narrow gaps in electronic components and between densely packed fibers such as carbon fibers and glass fibers. However, latent curing agents that meet these requirements have yet to be developed.

[0015] For example, Patent Document 1 discloses a liquid bisimidazole compound obtained by modifying imidazole with acrylate as a curing agent. However, this compound has a problem in that its storage stability leaves room for improvement.

[0016] Patent Document 2 discloses an amine imide compound obtained by using 1-aminopyrrolidine, but since it is a solid, it has a problem of poor permeability at room temperature.

[0017] Furthermore, Patent Document 3 discloses a liquid amine imide compound which uses 1,1-dimethylhydrazine, which is a self-reactive substance and designated as a toxic substance, as a raw material and therefore has a problem of being difficult to handle.

[0018] Therefore, in view of the above-mentioned problems of the conventional technology, an object of the present invention is to provide an amine imide compound having excellent permeability, curability and storage stability.

[0019] Solutions for solving problems

[0020] As a result of intensive research, the present inventors have discovered that an amine imide compound having a specific structure is excellent in permeability, curability, and storage stability, thereby completing the present invention.

[0021] That is, the present invention is as follows.

[0022] [1] An amine imide compound represented by the following formula (1), (2) or (3).

[0023]

[0024] (In formulas (1) to (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group optionally containing a hydroxyl group, a carbonyl group, an ester bond, or an ether bond and having 1 to 15 carbon atoms; R2 and R3 each independently represent an unsubstituted or substituted alkyl group, an aryl group, an aralkyl group, having 1 to 12 carbon atoms, or a heterocycle having 7 or less carbon atoms formed by linking R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group optionally containing an oxygen atom and having 1 to 30 carbon atoms; and n represents an integer from 1 to 3.)

[0025] [2] The amine imide compound according to [1] above, wherein the R1 in the formula (1) or (3) is a group represented by the following formula (4) or (5).

[0026]

[0027]

[0028] (In formula (4) and (5), R 11 Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms; and n each independently represents an integer from 0 to 6.

[0029] [3] The amine imide compound according to [1] above, wherein the R1 in the formula (2) is a group represented by the following formula (6) or (7).

[0030]

[0031] (In formula (6) and (7), R 12 and R 13 Each independently represents a single bond, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms.

[0032] [4] The amine imide compound according to any one of [1] to [3] above, wherein at least one of R2 and R3 represents an aralkyl group.

[0033] [5] The amine imide compound according to any one of [1] to [3] above, wherein the heterocyclic ring having 7 or less carbon atoms formed by connecting R2 and R3 is represented by the following formula (8), wherein R 23 and N in formula (1), (2) or (3) + The heterocyclic ring formed.

[0034]

[0035] (In formula (8), R 23 Indicates that N +Groups that together form a heterocyclic structure.)

[0036] [6] The amine imide compound according to any one of [1] to [5], wherein the R4 in the formula (1) or (2) is a linear or branched alkyl group having 3 to 12 carbon atoms, or a linear or branched alkenyl group having 3 to 6 carbon atoms.

[0037] [7] The amine imide compound according to any one of [1] to [5] above, wherein the R4 in the formula (3) is a group represented by the following formula (9) or (10).

[0038]

[0039] (In formula (9) and (10), R 41 and R 42 Each independently represents an alkyl group, an aryl group, or an aralkyl group having 1 to 5 carbon atoms; and n each independently represents an integer from 0 to 10.

[0040] [8] The amine imide compound according to any one of [1] to [7], wherein the amine imide compound is represented by the formula (2) or (3); and n is 2 or 3.

[0041] [9] The amine imide compound according to any one of [1] to [7] above, wherein the amine imide compound is represented by the formula (2) or (3) above; and n is 2.

[0042]

[10] The amine imide compound according to any one of [1] to [9] above, which has a viscosity at 25°C of 1300 Pa·s or less.

[0043]

[11] The amine imide compound according to any one of [1] to

[10] , wherein the top temperature (T peak ) and the starting temperature (T onset ) difference (T peak -T onset ) is below 45°C.

[0044]

[12] An amine imide composition comprising a plurality of amine imide compounds according to any one of [1] to

[11] above.

[0045]

[13] The amine imide composition according to

[12] above, comprising the amine imide compounds represented by the aforementioned formula (1) and the aforementioned formula (3).

[0046]

[14] A curing agent comprising the amine imide compound described in any one of [1] to

[10] above, or the amine imide composition described in

[12] or

[13] above.

[0047]

[15] An epoxy resin composition comprising an epoxy resin (α) and the curing agent (β) described in

[14] above.

[0048]

[16] The epoxy resin composition according to

[15] , wherein the content of the curing agent (β) is 1 to 50 parts by mass relative to 100 parts by mass of the epoxy resin (α).

[0049]

[17] The epoxy resin composition according to

[15] or

[16] , further comprising an acid anhydride curing agent (γ).

[0050]

[18] A method for producing an amine imide compound, which is a method for producing the amine imide compound described in any one of [1] to

[11] above, or the amine imide compound in the amine imide composition described in

[12] or

[13] above,

[0051] The method comprises a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B), and a glycidyl ether compound (C).

[0052]

[19] A sealing material which is a cured product of the epoxy resin composition according to any one of

[15] to

[17] .

[0053]

[20] An adhesive comprising the epoxy resin composition described in

[15] above, wherein the curing agent (β) comprises an amine imide compound represented by the formula (3).

[0054] Effects of the Invention

[0055] According to the present invention, a latent curing agent having excellent permeability, curability and storage stability can be provided. DETAILED DESCRIPTION

[0056] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. This embodiment is an illustration for illustrating the present invention and does not mean that the present invention is limited to the following contents. The present invention can be implemented by appropriately modifying the present invention within the scope of its main purpose.

[0057] 〔Amine imide compounds〕

[0058] The amine imide compound of this embodiment is represented by the following formula (1), (2) or (3).

[0059]

[0060] (In formulas (1) to (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group optionally containing a hydroxyl group, a carbonyl group, an ester bond, or an ether bond and having 1 to 15 carbon atoms; R2 and R3 each independently represent an unsubstituted or substituted alkyl group, an aryl group, an aralkyl group, having 1 to 12 carbon atoms, or a heterocycle having 7 or less carbon atoms formed by linking R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group optionally containing an oxygen atom and having 1 to 30 carbon atoms; and n represents an integer from 1 to 3.)

[0061] The amine imide compound of this embodiment does not have a substituent with curing properties in its original form. Therefore, even if it is compatible with epoxy resin at room temperature, it will not undergo an addition reaction with epoxy groups. However, as shown in the following reaction formula, heating causes the N-N bond to cleave, generating an acyl nitrene and a tertiary amine. The acyl nitrene then forms an isocyanate through a 1,2-transfer reaction. The isocyanate and tertiary amine generated here have curing properties and undergo an addition reaction with the epoxy group to achieve curing. In other words, the amine imide compound of this embodiment functions as a latent curing agent.

[0062]

[0063] Furthermore, the amine imide compound of this embodiment has a hydroxyl group. Therefore, as shown in the following reaction formula, the isocyanate generated by heating undergoes an addition reaction with the tertiary amine, resulting in a structure having a tertiary amine and a carbamate bond within a single molecule. This structure has superior curing properties compared to isocyanates and tertiary amines, and thus the amine imide compound of this embodiment functions as a latent curing agent with excellent curing properties.

[0064]

[0065] It should be noted that the compound represented by formula (2) is a compound in which the compound represented by formula (1) is linked via an n-valent linking group R1, and the compound represented by formula (3) is a compound in which the compound represented by formula (1) is linked via an n-valent linking group R4. In the case of the compound represented by formula (2), an n-valent isocyanate compound and a monovalent tertiary amine are generated by heating, while in the case of the compound represented by formula (3), a monovalent isocyanate compound and an n-valent tertiary amine are generated by heating.

[0066] The peak temperature (T peak) is preferably 100°C or higher and 250°C or lower, more preferably 100°C or higher and 220°C or lower, further preferably 100°C or higher and 200°C or lower, and even more preferably 100°C or higher and 180°C or lower.

[0067] By making T peak When the temperature is 100°C or higher, the storage stability tends to be further improved. peak The curing performance of the amine imide compound tends to be further improved when the temperature is 250°C or lower. peak ) is the apex temperature of the exothermic peak associated with the decomposition of the N-N bond, and refers to the peak temperature of the exothermic peak in differential thermal analysis.

[0068] In addition, the starting point temperature (T onset ) is preferably 80°C or higher and 200°C or lower, more preferably 80°C or higher and 185°C or lower, further preferably 80°C or higher and 170°C or lower, and even more preferably 80°C or higher and 160°C or lower.

[0069] By making T onset When the temperature is 80°C or higher, the storage stability tends to be further improved. onset The curing performance of the amine imide compound tends to be further improved when the temperature is 200°C or lower. onset ) refers to the starting point temperature of the exothermic peak in differential thermal analysis. More specifically, the intersection of the tangent line of the maximum slope of the starting point of the exothermic peak and the extension line of the baseline (bottom line) is set as the starting point temperature (T onset ).

[0070] The aforementioned peak temperature (T peak ) and the aforementioned starting temperature (T onset ) difference (T peak -T onset ) is preferably 45°C or lower, more preferably 40°C or lower, further preferably 35°C or lower, and further preferably 30°C or lower. peak -T onset ) is 45°C or less, so that the decomposition of the N-N bond by heating proceeds rapidly, and the urgency of the curing reaction tends to be further increased. peak -T onset ) is not particularly limited, but is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher.

[0071] Peak temperature (T peak ), starting temperature (T onset ) and the difference (T peak -T onset ) can be controlled by adjusting the functional groups of the amine imide compound of this embodiment. For example, there is a tendency for R1 to contribute to lowering the energy of N-N bond cleavage, while R2 and R3 contribute to lowering the energy of the cleavage reaction due to destabilization caused by steric hindrance. Therefore, by appropriately combining groups that contribute to improving curing performance and other groups as R1, R2, and R3, as described below, their temperatures can be controlled.

[0072] The amine imide compound of the present embodiment is preferably a compound that is liquid at room temperature.

[0073] In this embodiment, the viscosity at 25° C. can be used as an indicator indicating liquid at room temperature. The viscosity at 25° C. of the amine imide compound of this embodiment is preferably 1300 Pa·s or less, more preferably 900 Pa·s or less, further preferably 800 Pa·s or less, and even more preferably 700 Pa·s or less.

[0074] In addition, the lower limit of the viscosity at 25° C. is not particularly limited, but is preferably 0.01 Pa·s or more.

[0075] The amine imide compound of this embodiment is a liquid compound at room temperature. In particular, by setting the viscosity at 25° C. to 1300 Pa·s or less, the solubility and dispersibility in the epoxy resin composition and the permeability in the substrate are further improved.

[0076] It should be noted that the viscosity of the amine imide compound of the present embodiment can be controlled within the above numerical range by adjusting the functional groups of R1 to R4 in formulae (1) to (3).

[0077] It is believed that R1 in formula (1), (2), or (3) contributes to lowering the energy of cleavage of the N-N bond, R2 and R3 contribute to lowering the energy of the cleavage reaction due to instability caused by steric hindrance, and R4 contributes to liquidification of the compound and suppresses a decrease in the glass transition temperature of the resulting cured product, although these groups are not particularly limited. Details of each group are described below.

[0078] In formulas (1), (2), and (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or an nvalent organic group having 1 to 15 carbon atoms and optionally having a hydroxyl group, a carbonyl group, an ester bond, or an ether bond. Such an organic group is not particularly limited, and examples thereof include hydrocarbon groups, groups in which hydrogen atoms bonded to carbon atoms in a hydrocarbon group are substituted with hydroxyl groups or carbonyl groups, or groups in which some of the carbon atoms constituting a hydrocarbon group are replaced with ester bonds or ether bonds. Examples of such hydrocarbon groups include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl; alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, dodecenyl, hexadecenyl, and octadecenyl; aryl groups such as phenyl; and aralkyl groups such as methylphenyl, ethylphenyl, and propylphenyl, which are combinations of alkyl groups and phenyl groups.

[0079] The organic group represented by R1 may have other substituents. The substituents are not particularly limited, and examples thereof include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azido groups, thiol groups, sulfon groups, nitro groups, hydroxyl groups, acyl groups, and aldehyde groups.

[0080] The organic group represented by R1 has 1 to 15 carbon atoms, preferably 1 to 12, and more preferably 1 to 7. When the organic group represented by R1 has a carbon number within this range, a liquid amine imide compound satisfying the above-mentioned viscosity is easily obtained, and the curing performance of the amine imide compound is further improved. Furthermore, when the organic group represented by R1 has a carbon number within this range, the availability of raw materials is further improved.

[0081] Among the above, R1 in formula (1) or (3) is preferably a group represented by the following formula (4) or (5). By having such a group, there is a tendency that a liquid amine imide compound satisfying the above viscosity is easily obtained, and the curing performance of the amine imide compound is further improved.

[0082]

[0083] (In formula (4) and (5), R 11 Each independently represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms; and n each independently represents an integer from 0 to 6.

[0084] Among the above, the group in formula (5) where n is 0 or 1 is preferred. Thus, the compound represented by formula (1) or (3) has a diketone structure in the R1-C(=O)- structure. This diketone structure tends to further improve the curing properties of the amine imide compound.

[0085] It should be noted that R in formula (4) or (5) 11 The number of carbon atoms and n are adjusted so that the maximum number of carbon atoms of the group represented by formula (4) or (5) does not exceed 15.

[0086] In addition, R1 in formula (2) is preferably a group represented by the following formula (6) or (7). By having such a group, a liquid amine imide compound satisfying the above-mentioned viscosity can be easily obtained, and the curing performance of the amine imide compound is further improved.

[0087]

[0088] (In formula (6) and (7), R 12 and R 13 Each independently represents a single bond, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms.

[0089] Among the above, R in formula (7) is preferably 13 = is a single bond or a methyl group. Thus, the compound represented by formula (2) has a diketone structure in the R1-C(=O)- structure. This diketone structure tends to further improve the curing performance of the amine imide compound.

[0090] In formulae (1), (2) and (3), R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group, aralkyl group having 1 to 12 carbon atoms, or a heterocyclic ring having 7 or less carbon atoms formed by linking R2 and R3.

[0091] The alkyl group having 1 to 12 carbon atoms represented by R2 or R3 is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl. Furthermore, the above-mentioned alkyl groups may be a combination of a linear or branched alkyl group and a cyclic alkyl group. Furthermore, the above-mentioned alkyl groups may contain an unsaturated linking group.

[0092] The number of carbon atoms in the alkyl group represented by R2 or R3 is independently 1 to 12, preferably 2 to 10, and more preferably 5 to 10. Compounds such as dimethylhydrazine, where the alkyl group of the asymmetric dialkylhydrazine has a small number of carbon atoms, pose a risk of explosion and other toxicity to the human body. By setting the number of carbon atoms in the alkyl group represented by R2 or R3 to 2 or more, the use of raw materials with such toxic risks can be avoided. Furthermore, by setting the number of carbon atoms in the alkyl group represented by R2 or R3 to 5 or more, a liquid amine imide compound meeting the aforementioned viscosity can be readily obtained, and the curing properties of the amine imide compound can be further improved.

[0093] In addition, the aryl group represented by R2 or R3 is not particularly limited, and examples thereof include phenyl and naphthyl. Furthermore, the aralkyl group represented by R2 or R3 is not particularly limited, and examples thereof include methylphenyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl. Among them, at least one of R2 and R3 is preferably an aralkyl group, more preferably a methylphenyl (benzyl) group. As a result, there is a tendency for the curing performance of the amine imide compound to be further improved. It should be noted that the number of carbon atoms of the aryl group and aralkyl group represented by R2 or R3 is not particularly limited, and is preferably 6 to 20.

[0094] The substituent of the alkyl group, aryl group or aralkyl group represented by R2 or R3 is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a carbonyl group, a cyano group, an azo group, an azide group, a thiol group, a sulfone group, a nitro group, a hydroxyl group, an acyl group and an aldehyde group.

[0095] R2 and R3 are optionally linked to form a heterocyclic ring having 7 or less carbon atoms. Such a heterocyclic ring is not particularly limited, and examples thereof include a heterocyclic ring represented by the following formula (8): 23 and N in formula (1), (2) or (3) + It should be noted that R 23 It represents a group to which R2 and R3 are connected.

[0096]

[0097] (In formula (8), R 23 Indicates that N + Groups that together form a heterocyclic structure.)

[0098] As R 23 With N + The heterocyclic ring formed is not particularly limited, and examples thereof include four-membered rings such as azetidine ring; five-membered rings such as pyrrolidine ring, pyrrole ring, morpholine ring, and thiazine ring; six-membered rings such as piperidine ring; and seven-membered rings such as hexamethyleneimine ring and azepine ring.

[0099] Among them, the heterocyclic ring is preferably a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, or an azepine ring, and more preferably a six-membered ring or a seven-membered ring. The presence of such a group tends to facilitate obtaining a liquid amine imide compound satisfying the aforementioned viscosity, and further improves the curing performance of the amine imide compound.

[0100] In addition, as a substituent, there is no particular limitation, and examples thereof include an alkyl group, an aryl group, or a substituent in the above-mentioned R2 and R3. Furthermore, when the heterocyclic ring has an alkyl group as a substituent, examples thereof include an alkyl group adjacent to N + A methyl group bonded to a carbon atom, etc.

[0101] In formulas (1), (2), and (3), R4 represents a hydrogen atom, or a monovalent organic group or an n-valent organic group optionally containing an oxygen atom and having 1 to 30 carbon atoms. Such an organic group is not particularly limited, and examples thereof include hydrocarbon groups; groups in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted with a hydroxyl group, a carbonyl group, or a group containing a silicon atom; or groups in which a portion of the carbon atoms constituting the hydrocarbon group are replaced with an ester bond, an ether bond, or a silicon atom. Examples of such hydrocarbon groups include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl; alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, dodecenyl, hexadecenyl, and octadecenyl; aryl groups such as phenyl; or aralkyl groups formed by a combination of an alkyl group and a phenyl group such as methylphenyl, ethylphenyl, and propylphenyl.

[0102] The hydrocarbon group represented by R4 includes a bisphenol skeleton such as a bisphenol A skeleton, a bisphenol AP skeleton, a bisphenol B skeleton, a bisphenol C skeleton, a bisphenol E skeleton, and a bisphenol F skeleton. The organic group including the bisphenol skeleton is not particularly limited, and examples thereof include groups having a polyoxyalkylene group added to the hydroxyl group of each bisphenol skeleton.

[0103] Among these, the organic group shown in R4 in formula (1) or (2) is preferably alkyl, alkenyl, aralkyl, more preferably alkyl, alkenyl, further preferably branched alkyl and branched alkenyl.It should be noted that these preferred groups optionally have substituents.By having this group, thereby there is following tendency: easily obtain the liquid amine imide compound that satisfies above-mentioned viscosity, and the curing property of amine imide compound further improves.In addition, there is the tendency that Tg further improves in the cured product obtained using amine imide compound.

[0104] As described above, the organic group represented by R4 has a carbon number of 1 to 30, preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. By setting the carbon number of the organic group represented by R4 within the aforementioned range, it is easier to obtain a liquid amine imide compound that satisfies the aforementioned viscosity, and the curing performance of the amine imide compound is further improved. Furthermore, the Tg of the cured product obtained using the amine imide compound is further increased. Furthermore, by setting the carbon number of the organic group represented by R4 within the aforementioned range, the availability of raw materials is further improved.

[0105] Among the above, R4 in formula (1) or (2) is preferably a linear or branched alkyl group having 3 to 12 carbon atoms, or a linear or branched alkenyl group having 3 to 6 carbon atoms. The presence of such a group tends to facilitate obtaining a liquid amine imide compound satisfying the aforementioned viscosity, and further improves the curing performance of the amine imide compound.

[0106] In addition, R4 in formula (3) is preferably a group represented by the following formula (9) or (10). By having such a group, there is a tendency that a liquid amine imide compound satisfying the above-mentioned viscosity is easily obtained, and the curing performance of the amine imide compound is further improved.

[0107]

[0108] (In formula (9) and (10), R 41 and R 42 Each independently represents an alkyl group, an aryl group, or an aralkyl group having 1 to 5 carbon atoms; and n each independently represents an integer from 0 to 10.

[0109] The amine imide compound of this embodiment is represented by the above formula (2) or (3), wherein n in the formula (2) or (3) is preferably 2 or 3, and more preferably 2. This can improve curability.

[0110] [Amine imide composition]

[0111] The amine imide composition of the present embodiment comprises a plurality of amine imide compounds represented by the aforementioned formula (1), (2) or (3). From the viewpoint of controlling the curing temperature or controlling the viscosity, in order to obtain the effect of improving the properties, the amine imide composition is configured to comprise a plurality of amine imide compounds of the present embodiment. It should be noted that a plurality of amine imide compounds represented by the same formula but having different structures may be included.

[0112] In particular, from the viewpoint of controlling viscosity, an amine imide composition containing the amine imide compounds represented by the above formula (1) and formula (3) is preferred.

[0113] When a plurality of amine imide compounds are contained, the viscosity tends to be easily controlled by containing the amine imide compound represented by the above formula (1) in an amount of 0.1% by mass to 99.5% by mass.

[0114] In the case of an amine imide composition containing a plurality of amine imide compounds, the composition can be obtained by mixing the plurality of amine imide compounds. In the method for producing the amine imide compound described below, the composition can also be obtained by simultaneously producing the plurality of amine imide compounds.

[0115] [Method for producing amine imide compound and amine imide composition]

[0116] The method for producing the amine imide compound of the present embodiment is not particularly limited as long as it is a method for obtaining the amine imide compound having the above-mentioned structure.

[0117] The method for producing the amine imide composition of the present embodiment includes a method of mixing a plurality of amine imide compounds obtained by the method described below, and a method of simultaneously producing a plurality of amine imide compounds to obtain a mixture.

[0118] Examples of the method for producing the amine imide compound of the present embodiment include a method having a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B), and a glycidyl ether compound (C).

[0119] Hereinafter, the manufacturing method will be described.

[0120] The carboxylate compound (A) is not particularly limited, and examples thereof include monocarboxylate compounds and dicarboxylate compounds.

[0121] Specific examples of the monocarboxylic acid ester compound include methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonic acid, methyl benzoylformate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, and 4-tert-butoxybenzoylmethyl. In addition, ethyl esters and propyl esters may be used instead of these. Specific examples of the dicarboxylic acid ester compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartarate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaic acid, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate. Alternatively, diethyl esters, dipropyl esters, and the like may be used.

[0122] Among these, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate are preferred from the viewpoint of curability and liquidization.

[0123] Furthermore, among these, ethyl lactate, methyl mandelate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, and diethyl 1,3-acetonedicarboxylate are more preferred from the viewpoint of easy availability. The carboxylate compound (A) may be used alone or in combination of two or more.

[0124] The hydrazine compound (B) is not particularly limited, and examples thereof include dimethylhydrazine, diethylhydrazine, methylethylhydrazine, methylpropylhydrazine, methylbutylhydrazine, methylpentylhydrazine, methylhexylhydrazine, ethylpropylhydrazine, ethylbutylhydrazine, ethylpentylhydrazine, ethylhexylhydrazine, dipropylhydrazine, dibutylhydrazine, dipentylhydrazine, dihexylhydrazine, methylphenylhydrazine, ethylphenylhydrazine, methyltolylhydrazine, ethyltolylhydrazine, diphenylhydrazine, benzylphenylhydrazine, dibenzylhydrazine, dinitrophenylhydrazine, 1-aminopiperidine, N-aminohomopiperidine, 1-amino-2,6-dimethylpiperidine, 1-aminopyrrolidine, 1-amino-2-methylpyrrolidine, 1-amino-2-phenylpyrrolidine, and 1-aminomorpholine.

[0125] Among these, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred from the perspective of curability and liquefaction. Furthermore, among these, dibenzylhydrazine and 1-aminopiperidine are more preferred from the perspective of availability and safety. The hydrazine compound (B) may be used alone or in combination of two or more.

[0126] The glycidyl ether compound (C) is not particularly limited, and for example, a monofunctional monoglycidyl ether compound or a difunctional or higher polyglycidyl ether compound can be used. Specific examples of the monoglycidyl ether compound include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, o-phenylphenol glycidyl ether, benzyl glycidyl ether, biphenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, tert-butyldimethylsilyl glycidyl ether, and 3-[diethoxy(methyl)silyl]propyl glycidyl ether. Specific examples of the polyglycidyl ether compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, diglycerol Aliphatic polyglycidyl ethers such as polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether; alicyclic polyglycidyl ether compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ethylene oxide addition type bisphenol A diglycidyl ether, propylene oxide addition type bisphenol A diglycidyl ether, and hydrogenated products of these condensates; aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether, etc.

[0127] Among these, methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, ethylene oxide addition type bisphenol A type diglycidyl ether, and propylene oxide addition type bisphenol A type diglycidyl ether are preferred from the viewpoint of curability and liquidization.

[0128] Among these, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, trimethylolpropane polyglycidyl ether, ethylene oxide-added bisphenol A diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, and propylene oxide-added bisphenol A diglycidyl ether are more preferred from the viewpoints of availability and Tg of the cured product. The glycidyl ether compound (C) may be used alone or in combination of two or more.

[0129] The amounts of the carboxylate compound (A), hydrazine compound (B), and glycidyl ether compound (C) added to the reaction system can be expressed as a molar ratio of functional groups. The amount of carboxylate groups in the carboxylate compound (A) is preferably 0.8 to 3.0 moles, more preferably 0.9 to 2.8 moles, and even more preferably 0.95 to 2.5 moles per 1 mole of primary amine in the hydrazine compound (B). Furthermore, the amount of glycidyl groups in the glycidyl ether compound (C) is preferably 0.8 to 2.0 moles, more preferably 0.9 to 1.5 moles, and even more preferably 0.95 to 1.4 moles per 1 mole of primary amine in the hydrazine compound (B).

[0130] By controlling the amount of glycidyl groups added to the glycidyl ether compound (C) relative to 1 mol of the primary amine of the hydrazine compound (B), an amine imide composition containing the amine imide compounds represented by formula (1) and formula (3) can be simultaneously produced. Specifically, the amount of glycidyl groups added to the glycidyl ether compound (C) relative to 1 mol of the primary amine of the hydrazine compound (B) is preferably 0.1 to 3.0 mol, more preferably 0.3 to 2.0 mol, and even more preferably 0.5 to 1.0 mol.

[0131] In the method for producing the amine imide compound and amine imide composition of the present embodiment, the reaction of the components (A) to (C) proceeds even without using a solvent. However, from the viewpoint of uniform reaction, it is preferred to use a solvent.

[0132] The solvent is not particularly limited as long as it does not react with components (A) to (C), and examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and tert-butanol; and ethers such as tetrahydrofuran and diethyl ether.

[0133] The reaction temperature is preferably 10 to 70°C, more preferably 20 to 60°C. A reaction temperature of 10°C or higher tends to cause the reaction to proceed rapidly, leading to a higher purity of the resulting amine imide compound. Furthermore, a reaction temperature of 60°C or lower effectively suppresses the polymerization reaction of the glycidyl ether compounds (C), thereby tending to further improve the purity of the amine imide compound.

[0134] The reaction time is preferably 1 to 7 days, more preferably 1 to 6 days, and even more preferably 1 to 4 days.

[0135] After the reaction is completed, the obtained reactant can be purified by known purification methods such as washing, extraction, recrystallization, column chromatography, etc. For example, the reaction solution dissolved in an organic solvent can be washed with water and then the organic layer can be heated under normal pressure or reduced pressure to remove unreacted raw materials and organic solvent from the reaction solution and recover the amine imide compound. Furthermore, the obtained reactant can be purified by column chromatography to recover the amine imide compound.

[0136] The solvent used for washing is not particularly limited as long as it can dissolve the residue of the raw material, but hexane, pentane, and cyclohexane are preferred from the viewpoints of yield, purity, and ease of removal.

[0137] The organic solvent used in the extraction is not particularly limited as long as it can dissolve the target amine imide compound. From the viewpoint of yield, purity, and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred.

[0138] The filler used in column chromatography can be alumina, silica gel and other known substances. In addition, the developing solvent can be ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol and other known substances used alone or in combination.

[0139] 〔Curing agent〕

[0140] The curing agent of the present embodiment contains the amine imide compound or amine imide composition of the present embodiment described above.

[0141] The curing agent of this embodiment may contain other components in addition to the amine imide compound or the amine imide composition.

[0142] Other ingredients include inorganic fillers, flame retardants, core-shell rubber particles, silane coupling agents, release agents, pigments, and other compounding agents. When other ingredients are included in addition to the amine imide compound or amine imide composition of this embodiment, their content is preferably 90% by mass or less.

[0143] A preferred form of the amine imide compound of this embodiment is liquid at room temperature. In this case, it has excellent compatibility with epoxy resins and can be suitably used as an epoxy resin composition to which other components are added.

[0144] 〔Epoxy resin composition〕

[0145] The epoxy resin composition of the present embodiment comprises an epoxy resin (α) and the curing agent (β) of the present embodiment. The epoxy resin composition of the present embodiment may further contain other curing agents other than the amine imide compound and amine imide composition of the present embodiment, or optional components commonly known to be used in epoxy resin compositions for various purposes, as needed.

[0146] The epoxy resin (α) is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD ​​epoxy resin, bisphenol M epoxy resin, bisphenol P epoxy resin, tetrabromobisphenol A epoxy resin, biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, tetrabromobiphenyl epoxy resin, diphenyl ether epoxy resin, benzophenone epoxy resin, phenyl benzoate epoxy resin, diphenyl sulfide epoxy resin, and the like. Resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcinol type epoxy resin, methyl resorcinol type epoxy resin, catechol type epoxy resin, N,N-diglycidyl aniline type epoxy resin, ethylene oxide addition type bisphenol A type epoxy resin, propylene oxide addition type epoxy resin Bifunctional epoxy resins such as bisphenol A epoxy resin, ethylene oxide addition type bisphenol F epoxy resin, propylene oxide addition type bisphenol F epoxy resin; trifunctional epoxy resins such as trisphenol type epoxy resin, N, N-diglycidylaminobenzene type epoxy resin, o-(N, N-diglycidylamino)toluene type epoxy resin, triazine type epoxy resin, ethylene oxide addition type trisphenol type epoxy resin, propylene oxide addition type trisphenol type epoxy resin Epoxy resins; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane epoxy resins and diaminobenzene epoxy resins; polyfunctional epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, triphenylmethane epoxy resins, tetraphenylethane epoxy resins, dicyclopentadiene epoxy resins, naphthol aralkyl epoxy resins, and brominated phenol novolac epoxy resins; and alicyclic epoxy resins. These may be used alone or in combination of two or more. Furthermore, epoxy resins obtained by modifying these with isocyanates or the like may also be used in combination.

[0147] The epoxy resin composition of this embodiment can be used in combination with other curing agents other than the above-mentioned curing agent (β). As other curing agents, there are no particular limitations, and examples thereof include amine curing agents such as imidazoles, diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, triethylenetetramine, isophoronediamine, polyalkylene glycol polyamine, and polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine; amide curing agents such as dicyandiamide; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride Anhydride-based curing agents such as diformic anhydride; polyphenol compounds such as phenol novolac resins, cresol novolac resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, biphenyl-modified phenolic resins, biphenyl-modified phenolic aralkyl resins, dicyclopentadiene-modified phenolic resins, aminotriazine-modified phenolic resins, naphthol novolac resins, naphthol-phenol co-condensation novolac resins, and naphthol-cresol co-condensation novolac resins, as well as their modified products; BF3-amine complexes, guanidine derivatives, etc. These curing agents may be used alone or in combination of two or more.

[0148] When permeability is important among other curing agents other than the curing agent (β), it is preferred to further contain an acid anhydride curing agent (γ).

[0149] In the epoxy resin composition of the present embodiment, the content of the curing agent (β) when used as a curing agent is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 2 to 20 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin (α). By setting the content of the curing agent (β) within the above range, there is a tendency to fully promote the curing reaction and obtain better cured physical properties.

[0150] In the epoxy resin composition of the present embodiment, when a curing agent other than the curing agent (β) is contained and the curing agent (β) is used as a curing accelerator, the content of the curing agent (β) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass relative to 100 parts by mass of the total amount of the epoxy resin (α). By setting the content of the curing agent (β) as a curing accelerator within the above range, there is a tendency for the curing agent (β) to function as a curing catalyst for the other curing agents, sufficiently promote the curing reaction, and obtain better cured physical properties.

[0151] In the epoxy resin composition using the curing agent (β) containing the amine imide compound of the present embodiment as a curing accelerator and the above-mentioned acid anhydride curing agent (γ) as a curing agent, the equivalent ratio (acid anhydride group / epoxy group) of the acid anhydride curing agent (γ) to the epoxy group of the epoxy resin (α) is preferably 0.80 to 1.20, more preferably 0.85 to 1.15, and even more preferably 0.90 to 1.10.

[0152] By setting the usage-amounts of the epoxy resin (α) and the acid anhydride curing agent (γ) within the above-mentioned ranges, the curing reaction tends to be sufficiently promoted, and better cured properties tend to be obtained.

[0153] The epoxy resin composition of the present embodiment may further contain an inorganic filler as needed. Examples of the inorganic filler include, but are not particularly limited to, fused silica, crystalline silica, alumina, talc, silicon nitride, and aluminum nitride.

[0154] In the epoxy resin composition of the present embodiment, the content of the inorganic filler is not particularly limited as long as it is within the range that can obtain the effect of the present embodiment. In the epoxy resin composition of the present embodiment, the content of the inorganic filler is generally preferably 90% by mass or less. By setting the content of the inorganic filler to the above range, there is a tendency that the viscosity of the epoxy resin composition is sufficiently low and the handleability is excellent.

[0155] The epoxy resin composition of the present embodiment may further contain other compounding agents such as flame retardants, silane coupling agents, release agents, pigments, etc. as needed. As long as they are within the range that can achieve the effect of the present embodiment, suitable substances can be appropriately selected. As flame retardants, there are no particular limitations, and examples include halides, compounds containing phosphorus atoms, compounds containing nitrogen atoms, inorganic flame retardant compounds, etc.

[0156] 〔Cured product〕

[0157] The epoxy resin composition of the present embodiment is cured to obtain a cured product. The cured product of the epoxy resin composition of the present embodiment can be obtained by, for example, thermally curing the epoxy resin composition using a conventionally known method. For example, first, the epoxy resin, curing agent, and, as required, a curing accelerator, an inorganic filler, and / or a compounding agent are fully mixed until uniform to obtain an epoxy resin composition. Thereafter, the epoxy resin composition is formed using an injection mold or a transfer molding machine, a compression molding machine, an injection molding machine, etc., and further heated at about 80 to 200° C. and for about 2 to 10 hours to obtain a cured product.

[0158] Alternatively, a cured product can be obtained using, for example, the following method. First, the epoxy resin composition of the present embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone to obtain a solution. The resulting solution is then impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg. Subsequently, the resulting prepreg is subjected to heat and pressure molding to obtain a cured product.

[0159] 〔use〕

[0160] The epoxy resin composition of this embodiment and its cured product can be used in various applications where epoxy resin is used as a material, and are particularly useful as sealing materials, semiconductor sealing materials, adhesives, printed circuit boards, coatings, composite materials, and the like.

[0161] Among these, semiconductor sealing materials such as bottom filling and molding can be suitably used; conductive adhesives such as anisotropic conductive film (ACF); printed wiring boards such as solder resist layers and cover films; composite materials such as prepregs made by impregnating epoxy resin compositions into glass fibers or carbon fibers.

[0162] (Adhesive)

[0163] The adhesive of this embodiment preferably comprises the epoxy resin composition of this embodiment, and the curing agent (β) preferably comprises an amine imide compound represented by the formula (3). This can improve the permeability.

[0164] (Electronic components)

[0165] Cured products of the epoxy resin composition of this embodiment can be used in various electronic components. Examples include, but are not limited to, semiconductor encapsulants such as underfill and molding materials; conductive adhesives such as ACFs; printed wiring boards such as solder resists and coverlays; and composite materials such as prepregs impregnated with glass fibers, carbon fibers, and the like.

[0166] Example

[0167] Next, the present invention will be described in more detail with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto at all.

[0168] In addition, unless otherwise specified, the "parts" and "%" below are based on mass.

[0169] In the synthesis examples described below, amine imide compounds and amine imide compositions were synthesized. The physical properties of the amine imide compounds and amine imide compositions were measured for viscosity at 25° C., melting point, and infrared absorption spectrum.

[0170] [Method for measuring viscosity at 25°C]

[0171] The viscosity (Pa·s) of the amine imide compound at 25° C. was measured by dropping the amine imide compound and the amine imide composition (about 0.3 mL) into a measuring cup and measuring the viscosity using an E-type viscometer (“TVE-35H” manufactured by Toki Sangyo Co., Ltd.) 15 minutes after the sample temperature reached 25° C.

[0172] In addition, in Table 1, "properties" show the state at 25°C.

[0173] [Method for measuring melting point]

[0174] The melting point was measured only for substances that were solid at room temperature (25° C.) The melting point of the amine imide compound and the amine imide composition was defined as the top temperature of the endothermic peak under the following conditions.

[0175] · Apparatus: Differential thermal and thermogravimetric simultaneous measurement apparatus ("TG / DTA7220" manufactured by Hitachi High-Technologies Corporation)

[0176] Sample mass: about 10 mg

[0177] Sample container: open aluminum pot

[0178] ·Measurement temperature: 40℃~240℃

[0179] Heating rate: 5℃ / min

[0180] Atmosphere gas: nitrogen

[0181] Gas flow rate: 40mL / min

[0182] [Method for determining the decomposition temperature of the N-N bond]

[0183] The NN bond decomposition peak temperature of the amine imide compound and the amine imide composition is set as the peak temperature (T peak The N-N bond decomposition starting temperature is set as the starting temperature of the exothermic peak (T onset It should be noted that the starting temperature (T onset ) is obtained from the intersection of the tangent line of the maximum slope of the starting point of the exothermic peak and the extension line of the baseline (bottom line). Based on these, (T peak -T onset ).

[0184] <Measurement Conditions>

[0185] · Apparatus: Differential thermal and thermogravimetric simultaneous measurement apparatus ("TG / DTA7220" manufactured by Hitachi High-Technologies Corporation)

[0186] Sample mass: about 10 mg

[0187] Sample container: open aluminum pot

[0188] ·Measurement temperature: 40℃~240℃

[0189] Heating rate: 5℃ / min

[0190] Atmosphere gas: nitrogen

[0191] Gas flow rate: 40mL / min

[0192] [Measurement method of infrared absorption spectrum]

[0193] Infrared absorption spectra were measured using a Fourier transform infrared spectrophotometer ("FT / IR-410" manufactured by JASCO Corporation). Measurement samples were prepared using a liquid film method when the sample was liquid and a tablet method when the sample was solid.

[0194] The liquid film method is a method of sandwiching a sample with a rock salt plate that transmits infrared light to create a film-shaped measurement sample.

[0195] The tablet method is a method in which a sample is uniformly dispersed in potassium bromide powder using a mortar or the like, and then pressed to prepare a tablet-shaped measurement sample.

[0196] Confirm whether there is a 1570cm -1 ~1620cm -1 The specific infrared absorption spectrum derived from the amine imide group was observed at .

[0197] [Measurement method by mass spectrometry]

[0198] The mass spectrometry measurement was performed using a QDa detector manufactured by Waters as a mass spectrometry (MS) detector.

[0199] Acetonitrile was used as a measurement sample and the concentration was adjusted to about 0.25% by mass.

[0200] The liquid feeding conditions were initially 90:10 = methanol: water and changed to 50:50 = methanol: water after 3 minutes. A peak was observed at about 0.1 to 0.5 minutes, and analysis was performed on this peak.

[0201] The mass spectrometry analysis conditions of the Waters QDa detector were set as follows: Mass (m / z) ES+ 50-1250, capillary voltage 0.8 V, cone voltage 25 V, and probe temperature 600°C.

[0202] Each compound uses the addition of H + The m / z of 1 was observed.

[0203] A 5 mM ammonium acetate / methanol solution was delivered at 0.45 mL / min to promote ionization.

[0204] In the following, amine imide compounds and amine imide compositions are prepared.

[0205] It should be noted that the following synthesis examples are specific examples of the amine imide compounds and amine imide compositions of the present invention.

[0206] [Synthesis example 1]

[0207] 17.68 g (0.12 mol) of dimethyl succinate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 26.12 g (0.35 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials to obtain a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 44.37 g (yield: 92.3%) of a light yellow liquid amine imide compound A (Compound A). The infrared absorption spectrum measurement method described above yielded IR (neat): 1573 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 401.5 was observed. It was found that the amine imide compound A represented by the following formula was obtained.

[0208]

[0209] [Synthesis example 2]

[0210] 17.68 g (0.12 mol) of dimethyl succinate, 12.02 g (0.12 mol) of 1-aminopiperidine, 12.09 g (0.04 mol) of trimethylolpropane polyglycidyl ether, and 20.90 g (0.28 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 3 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials to obtain a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 33.46 g (yield: 88.5%) of a light yellow viscous amine imide compound B (compound B). The infrared absorption spectrum measurement method described above yielded IR (neat): 1576 cm -1The measured value of . In mass spectrometry analysis, a peak of m / z = 946.8 was observed. It was found that the amine imide compound B represented by the following formula was obtained.

[0211]

[0212] [Synthesis example 3]

[0213] 19.70 g (0.12 mol) of methyl benzoylformate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 27.13 g (0.37 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials to obtain a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 47.67 g (yield: 94.9%) of a light brown liquid amine imide compound C (Compound C). The infrared absorption spectrum measurement method described above yielded IR (neat): 1595 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 419.5 was observed. It was found that the amine imide compound C represented by the following formula was obtained.

[0214]

[0215] [Synthesis Example 4]

[0216] 24.27 g (0.12 mol) of diethyl 1,3-acetone dicarboxylate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 29.42 g (0.40 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 44.93 g (yield: 84.6%) of a dark brown liquid amine imide compound D (compound D). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1609 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 443.4 was observed. It was found that the amine imide compound D represented by the following formula was obtained.

[0217]

[0218] [Synthesis example 5]

[0219] 12.13 g (0.06 mol) of diethyl 1,3-acetone dicarboxylate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 23.35 g (0.32 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 3 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove the unreacted raw material residue to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 33.40 g (yield: 81.5%) of dark brown liquid amine imide compound E (compound E). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1586 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 683.9 was observed. It was found that the amine imide compound E represented by the following formula was obtained.

[0220]

[0221] [Synthesis example 6]

[0222] 14.17 g (0.12 mol) of dimethyl oxalate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 24.37 g (0.33 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 3 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 42.51 g (yield: 95.1%) of a light yellow liquid amine imide compound F (compound F). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1612 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 372.5 was observed. It was found that the amine imide compound F represented by the following formula was obtained.

[0223]

[0224] [Synthesis Example 7]

[0225] 7.09 g (0.06 mol) of dimethyl oxalate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 20.83 g (0.28 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 33.70 g (yield: 89.6%) of a light yellow viscous amine imide compound G (compound G). The infrared absorption spectrum measurement method described above yielded IR (neat): 1617 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 627.8 was observed. It was found that the amine imide compound G represented by the following formula was obtained.

[0226]

[0227] [Synthesis example 8]

[0228] 19.70 g (0.12 mol) of methyl benzoylformate, 12.02 g (0.12 mol) of 1-aminopiperidine, 13.70 g (0.12 mol) of allyl glycidyl ether, and 22.71 g (0.31 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 37.54 g (yield 90.3%) of brown liquid amine imide compound H (compound H). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1588 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 347.4 was observed. It was found that the amine imide compound H represented by the following formula was obtained.

[0229]

[0230] [Synthesis Example 9]

[0231] 7.46 g (0.045 mol) of methyl benzoylformate, 5.01 g (0.05 mol) of 1-aminopiperidine, 5.06 g (0.025 mol) of 1,4-butanediol diglycidyl ether, and 5.5 g (0.12 mol) of ethanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 1 day to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 16.21 g (yield: 89.5%) of a yellow liquid amine imide compound L (compound L). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1595 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 667.6 was observed. It was found that the amine imide compound L represented by the following formula was obtained.

[0232]

[0233] [Synthesis Example 10]

[0234] 7.46 g (0.045 mol) of methyl benzoylformate, 5.14 g (0.05 mol) of 1-aminopiperidine, 5.76 g (0.025 mol) of 1,6-hexanediol diglycidyl ether, and 5.5 g (0.12 mol) of ethanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 1 day to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was repeatedly washed with hexane to remove the unreacted raw material residue to obtain an organic layer. The organic layer was again concentrated under reduced pressure at 55°C to obtain 17.07 g (yield: 88.1%) of a reddish-brown liquid amine imide compound M (compound M). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1596 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 695.6 was observed. It was found that the amine imide compound M represented by the following formula was obtained.

[0235]

[0236] [Synthesis Example 11]

[0237] 7.86 g (0.065 mol) of ethyl lactate, 7.01 g (0.07 mol) of 1-aminopiperidine, 13.04 g (0.07 mol) of 2-ethylhexyl glycidyl ether and 7.7 g (0.17 mol) of ethanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 1 day to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off ethanol, by-product alcohol and unreacted raw materials, thereby obtaining a liquid product. The product was repeatedly washed with hexane to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 19.55 g (yield: 83.9%) of a light yellow liquid amine imide compound N (Compound N). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1592 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 359.5 was observed. It was found that the amine imide compound N represented by the following formula was obtained.

[0238]

[0239] [Synthesis Example 12]

[0240] 4.68 g (0.040 mol) of ethyl lactate, 4.41 g (0.044 mol) of 1-aminopiperidine, 5.06 g (0.022 mol) of 1,6-hexanediol diglycidyl ether, and 5.5 g (0.12 mol) of ethanol were mixed to obtain a solution. The solution was reacted while stirring at 55°C for 2 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product was repeatedly washed with hexane to remove unreacted raw material residues to obtain an organic layer. The organic layer was again concentrated under reduced pressure at 55°C to obtain 12.22 g (yield: 85.7%) of a light yellow liquid amine imide compound O (compound O). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1592 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 574.8 was observed. It was found that the amine imide compound O represented by the following formula was obtained.

[0241]

[0242] [Synthesis Example 13]

[0243] 3.54 g (0.030 mol) of ethyl lactate, 3.01 g (0.030 mol) of 1-aminopiperidine, 6.91 g (0.030 mol) of 1,6-hexanediol diglycidyl ether and 8.0 g (0.17 mol) of ethanol were mixed to obtain a solution. The solution was reacted while stirring at 55°C for 2 days to obtain a reaction liquid. The product was repeatedly washed with hexane to remove the unreacted raw material residue to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain a mixture of two amine imide compounds represented by the following formula, i.e., 12.01 g of a yellow liquid amine imide composition O2 (compound O2). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1593 cm -1 Measured values. Mass spectrometry revealed peaks at m / z = 575.6 and 421.4. m / z = 575.6 represents the same structure as amine imide compound O, while m / z = 421.4 represents a compound having a diol terminal structure on one side. This indicates that an amine imide composition O2 represented by the following formula was obtained.

[0244]

[0245] [Synthesis Example 14]

[0246] 5.32 g (0.045 mol) of ethyl lactate, 4.51 g (0.045 mol) of 1-aminopiperidine, 6.91 g (0.030 mol) of 1,6-hexanediol diglycidyl ether and 8.0 g (0.17 mol) of ethanol were mixed to obtain a solution. The solution was reacted while stirring at 55°C for 2 days to obtain a reaction liquid. The product was repeatedly washed with hexane to remove the unreacted raw material residue to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain a mixture of two amine imide compounds represented by the following formula, i.e., 14.56 g of a yellow liquid amine imide composition O3 (compound O3). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1592 cm -1 Measured values. Mass spectrometry revealed peaks at m / z = 575.6 and 421.4. m / z = 575.6 represents the same structure as amine imide compound O, while m / z = 421.4 represents a compound having a diol terminal structure on one side. This indicates that an amine imide composition O3 represented by the following formula was obtained.

[0247]

[0248] [Synthesis Example 15]

[0249] 3.64 g (0.022 mol) of D,L-methyl benzyl alcohol, 2.34 g (0.023 mol) of 1-aminopiperidine, 4.35 g (0.023 mol) of 2-ethylhexyl glycidyl ether and 3.0 g (0.07 mol) of ethanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 1 day to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off ethanol, by-product alcohol and unreacted raw materials, thereby obtaining a liquid product. The product was repeatedly washed with hexane to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 8.41 g (yield 90.5%) of a light yellow liquid amine imide compound P (compound P). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1603 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 421.5 was observed. It was found that the amine imide compound P represented by the following formula was obtained.

[0250]

[0251] [Synthesis Example 16]

[0252] 9.97 g (0.060 mol) of D, L-phenylenediol methyl ester, 6.01 g (0.06 mol) of 1-aminopiperidine, 6.91 g (0.03 mol) of 1,6-hexanediol diglycidyl ether, and 8.0 g (0.17 mol) of ethanol were mixed to obtain a solution. The solution was reacted while stirring at 55°C for 2 days to obtain a reaction liquid. The product was repeatedly washed with hexane to remove the unreacted raw material residue to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 22.76 g (yield: 87.3%) of a light yellow liquid amine imide compound Q (compound Q). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1603 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 699.7 was observed. It was found that the amine imide compound Q represented by the following formula was obtained.

[0253]

[0254] [Synthesis Example 17]

[0255] 2.52 g (0.015 mol) of D, L-phenylenediol methyl ester, 1.5 g (0.015 mol) of 1-aminopiperidine, 2.30 g (0.01 mol) of 1,6-hexanediol diglycidyl ether and 3.0 g (0.7 mol) of ethanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 1 day to obtain a reaction liquid. The product was repeatedly washed with hexane to remove the unreacted raw material residue and obtain an organic layer. The organic layer was again concentrated under reduced pressure at 55°C to obtain a mixture of two amine imide compounds represented by the following formula, i.e., 4.91 g of a light yellow liquid amine imide composition Q2 (compound Q2). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1600 cm -1 The measured value was . In mass spectrometry, peaks at m / z = 699.7 and 483.4 were observed. m / z = 699.7 indicates the same structure as amine imide compound Q, and m / z = 483.4 indicates a compound having a diol terminal structure on one side. This indicates that amine imide composition Q2 represented by the following formula was obtained.

[0256]

[0257] [Synthesis Example 18]

[0258] 2.92 g (0.02 mol) of dimethyl succinate, 2.01 g (0.02 mol) of 1-aminopiperidine, 3.73 g (0.02 mol) of 2-ethylhexyl glycidyl ether and 4.0 g (0.09 mol) of ethanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 1 day to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off ethanol, by-product alcohol and unreacted raw materials, thereby obtaining a liquid product. The product was repeatedly washed with hexane to remove unreacted raw material residues to obtain an organic layer. The organic layer was again concentrated under reduced pressure at 55°C to obtain 4.87 g (yield: 60.7%) of a light yellow liquid amine imide compound R (compound R). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1578 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 401.5 was observed. It was found that the amine imide compound R represented by the following formula was obtained.

[0259]

[0260] [Synthesis Example 19]

[0261] 4.38 g (0.03 mol) of dimethyl succinate, 3.00 g (0.03 mol) of 1-aminopiperidine, 3.45 g (0.015 mol) of 1,6-hexanediol diglycidyl ether and 4.0 g (0.09 mol) of ethanol were mixed to obtain a solution. The solution was reacted while stirring at 55°C for 1 day to obtain a product. The product was repeatedly washed with hexane to remove the unreacted raw material residue to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 10.06 g (yield: 81.3%) of a light yellow liquid amine imide compound S (compound S). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat): 1578 cm -1 In mass spectrometry analysis, a peak at m / z = 659.7 was observed.

[0262] It was found that the amine imide compound S represented by the following formula was obtained.

[0263]

[0264] [Synthesis Example 20]

[0265] 3.28 g (0.023 mol) of dimethyl succinate, 2.25 g (0.023 mol) of 1-aminopiperidine, 3.45 g (0.015 mol) of 1,6-hexanediol diglycidyl ether and 4.0 g (0.09 mol) of ethanol were mixed to obtain a solution. The solution was reacted while stirring at 55°C for 1 day to obtain a product. The product was repeatedly washed with hexane to remove the unreacted raw material residue to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain a mixture of two amine imide compounds represented by the following formula, i.e., 8.31 g of a light yellow liquid amine imide composition S2 (compound S2). Utilizing the aforementioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1578 cm -1 The measured value was . In mass spectrometry, peaks at m / z = 659.6 and 477.5 were observed. m / z = 659.6 is the same structure as the amine imide compound O, and m / z = 477.5 is a compound having a diol terminal structure on one side. Thus, the amine imide composition S2 represented by the following formula was obtained.

[0266]

[0267] [Synthesis Example 21]

[0268] 2.93 g (0.020 mol) of dimethyl succinate, 2.00 g (0.020 mol) of 1-aminopiperidine, 4.61 g (0.020 mol) of 1,6-hexanediol diglycidyl ether and 4.0 g (0.09 mol) of ethanol were mixed to obtain a solution. The solution was reacted while stirring at 55°C for 1 day to obtain a product. The product was repeatedly washed with hexane to remove the unreacted raw material residue to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain a mixture of two amine imide compounds represented by the following formula, i.e., 7.31 g of a light yellow liquid amine imide composition S3 (compound S3). Using the above-mentioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1578 cm -1 The measured value was . In mass spectrometry analysis, peaks at m / z = 659.6 and 477.5 were observed. m / z = 659.6 is the same structure as the amine imide compound O, and m / z = 477.5 is a compound having a diol terminal structure on one side. Thus, the amine imide composition S3 represented by the following formula was obtained.

[0269]

[0270] [Synthesis Example 22]

[0271] 14.18 g (0.12 mol) of ethyl lactate, 12.02 g (0.12 mol) of 1-aminopiperidine, 13.70 g (0.12 mol) of allyl glycidyl ether, and 19.95 g (0.27 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 3 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a solid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again at 55°C to obtain 29.14 g (yield 84.8%) of a light yellow crystalline solid amine imide compound I (Compound I). Using the aforementioned infrared absorption spectrum measurement method, IR (KBr): 1592 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 287.4 was observed. It was found that the amine imide compound I represented by the following formula was obtained.

[0272]

[0273] [Synthesis Example 23]

[0274] 19.94 g (0.12 mol) of DL-methyl benzyl alcohol, 12.02 g (0.12 mol) of 1-aminopiperidine, 13.70 g (0.12 mol) of allyl glycidyl ether, and 22.83 g (0.31 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a solid product. The product was recrystallized from ethyl acetate to obtain 30.11 g (yield: 72.0%) of a white crystalline solid amine imide compound J (Compound J). The infrared absorption spectrum measurement method described above yielded IR (KBr): 1594 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 349.3 was observed. It was found that the amine imide compound J represented by the following formula was obtained.

[0275]

[0276] [Synthesis example 24]

[0277] 8.77 g (0.06 mol) of dimethyl succinate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 21.67 g (0.29 mol) of tert-butanol were mixed to obtain a solution. The solution was reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid was concentrated under reduced pressure at 55°C to distill off tert-butanol, by-product alcohol, and unreacted raw materials, thereby obtaining a solid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw material residues. The organic layer was concentrated under reduced pressure again at 55°C to obtain 33.05 g (yield: 84.1%) of a white non-crystalline solid amine imide compound K (compound K). Using the aforementioned infrared absorption spectrum measurement method, IR (KBr): 1570 cm -1 The measured value of . In mass spectrometry analysis, a peak of m / z = 655.8 was observed. It was found that the amine imide compound K represented by the following formula was obtained.

[0278]

[0279] [Comparative Synthesis Example 1]

[0280] 13.22 g (0.12 mol) of 2-ethyl-4-methylimidazole and 22.11 g (0.12 mol) of 2-ethylhexyl acrylate were mixed to obtain a solution. The solution was reacted while stirring at 120°C for 4 hours to obtain a liquid product. The product was dissolved in ethyl acetate and repeatedly washed with water using a separatory funnel to remove unreacted raw materials, obtaining an organic layer. The organic layer was concentrated under reduced pressure at 55°C to obtain 33.46 g (yield: 33.46%) of a yellow liquid acrylate-imidazole adduct represented by the following formula. Mass spectrometry analysis revealed a peak at m / z = 294.4.

[0281]

[0282] The evaluation results of Synthesis Examples 1 to 24 and Comparative Synthesis Example 1 are shown in Table 1 below.

[0283] [Table 1]

[0284]

[0285] Next, epoxy resin compositions containing the amine imide compounds and amine imide compositions of [Synthesis Examples 1 to 24] and the acrylate-imidazole adduct of [Comparative Synthesis Example 1] as a curing agent were prepared.

[0286] The epoxy resin composition was measured for various properties, namely, curability and storage stability at room temperature (25° C.).

[0287] [Preparation of epoxy resin composition (1)]

[0288] The epoxy resin compositions prepared in the following Examples and Comparative Examples used the following epoxy resins as raw materials.

[0289] Epoxy resin: "BE-186EL" from Chang Chun Plastics Co., Ltd.

[0290] When mixing the various raw materials, the amine imide compound, amine imide composition, or acrylate-imidazole adduct is added so that the amount is 2 to 20 parts by mass relative to 100 parts by mass of the epoxy resin. The epoxy resin and the amine imide compound, amine imide composition, or acrylate-imidazole adduct are placed in a plastic stirring container, and the mixture is stirred and mixed using a rotary / revolving stirrer ("ARE-310" manufactured by THINKY) to prepare an epoxy resin composition.

[0291] [Evaluation method of curability (1)]

[0292] As a method for evaluating curability (1), 10 mg of the prepared epoxy resin composition was weighed into an aluminum container of a differential scanning calorimeter ("DSC220C" manufactured by SII Corporation), heated in an oven at 200°C for 3 hours, and then rapidly cooled. The reaction rate was calculated based on the change in DSC heat release before and after heating, and the curability was evaluated based on the reaction rate.

[0293] A reaction rate of 95% or more was evaluated as "⊚", a reaction rate of less than 95% but 90% or more was evaluated as "○", a reaction rate of less than 90% but 80% or more was evaluated as "Δ", and a reaction rate of less than 80% was evaluated as "×".

[0294] [Evaluation method for storage stability (1)]

[0295] As a storage stability evaluation method (1), the viscosity of the epoxy resin composition at 25°C immediately after preparation is recorded as "η1", and the viscosity of the epoxy resin composition at 25°C stored in a constant temperature bath at 25°C for 3 days is recorded as "η2". The value calculated by η2 / η1 is obtained as the viscosity increase ratio, and the storage stability at room temperature is evaluated based on the viscosity increase ratio.

[0296] The viscosity increase ratio was judged as “⊚” when it was less than 1.5 times, “◯” when it was 1.5 times or more and less than 2.0 times, “△” when it was 2.0 times or more and less than 3.0 times, and “×” when it was 3.0 times or more.

[0297] [Example 1]

[0298] 20 g of an epoxy resin ("BE-186EL" manufactured by Chang Chun Plastics Co., Ltd.) and 1.6 g of an amine imide compound A were placed in a plastic stirring container and stirred and mixed using a rotation / revolution stirrer ("ARE-310" manufactured by THINKY Corporation) to prepare an epoxy resin composition. The curability was evaluated using the curability evaluation method (1) described above, and the storage stability at room temperature was evaluated using the storage stability evaluation method (1) described above.

[0299] [Example 2]

[0300] Except having changed the addition amount of the amine imide compound A into 6.0 g, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0301] [Example 3]

[0302] An epoxy resin composition was prepared in the same manner as in Example 1 except that the amine imide compound A was changed to the amine imide compound B and the amount of the amine imide compound B added was changed to 2.0 g, and the curability and storage stability at room temperature were evaluated.

[0303] [Example 4]

[0304] An epoxy resin composition was prepared in the same manner as in Example 1 except that the amine imide compound A was changed to the amine imide compound C and the amount of the amine imide compound C added was changed to 6.0 g, and the curability and storage stability at room temperature were evaluated.

[0305] [Example 5]

[0306] An epoxy resin composition was prepared in the same manner as in Example 1 except that the amine imide compound A was changed to the amine imide compound C and the amount of the amine imide compound C added was changed to 0.4 g, and the curability and storage stability at room temperature were evaluated.

[0307] [Example 6]

[0308] Except having changed the amine imide compound A into the amine imide compound C, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0309] [Example 7]

[0310] Except having changed the amine imide compound A into the amine imide compound D, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0311] [Example 8]

[0312] Except having changed the amine imide compound A into the amine imide compound E, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0313] [Example 9]

[0314] Except having changed the amine imide compound A into the amine imide compound F, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0315] [Example 10]

[0316] Except having changed the amine imide compound A into the amine imide compound G, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0317] [Example 11]

[0318] Except having changed the amine imide compound C into the amine imide compound H, it carried out similarly to Example 5, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0319] [Example 12]

[0320] Except having changed the amine imide compound A into the amine imide compound H, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0321] [Example 13]

[0322] Except having changed the amine imide compound A into the amine imide compound L, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0323] [Example 14]

[0324] Except having changed the amine imide compound A into the amine imide compound M, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0325] [Example 15]

[0326] Except having changed the amine imide compound A into the amine imide compound N, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0327] [Example 16]

[0328] Except having changed the amine imide compound A into the amine imide compound N, it carried out similarly to Example 2, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0329] [Example 17]

[0330] Except having changed the amine imide compound A into the amine imide compound O, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0331] [Example 18]

[0332] Except having changed the amine imide compound A into the amine imide compound O, the epoxy resin composition was prepared similarly to Example 2, and the curability and storage stability at room temperature were evaluated.

[0333] [Example 19]

[0334] Except having changed the amine imide compound A into the amine imide composition O2, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0335] [Example 20]

[0336] Except having changed the amine imide compound A into the amine imide composition O3, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0337] [Example 21]

[0338] Except having changed the amine imide compound A into the amine imide composition O3, the epoxy resin composition was prepared similarly to Example 2, and the curability and storage stability at room temperature were evaluated.

[0339] [Example 22]

[0340] Except having changed the amine imide compound A into the amine imide compound P, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0341] [Example 23]

[0342] Except having changed the amine imide compound A into the amine imide compound Q, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0343] [Example 24]

[0344] Except having changed the amine imide compound A into the amine imide composition Q2, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0345] [Example 25]

[0346] Except having changed the amine imide compound A into the amine imide compound R, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0347] [Example 26]

[0348] Except having changed the amine imide compound A into the amine imide compound R, the epoxy resin composition was prepared similarly to Example 2, and the curability and storage stability at room temperature were evaluated.

[0349] [Example 27]

[0350] Except having changed the amine imide compound A into the amine imide compound S, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0351] [Example 28]

[0352] Except having changed the amine imide compound A into the amine imide compound S, the epoxy resin composition was prepared similarly to Example 2, and the curability and storage stability at room temperature were evaluated.

[0353] [Example 29]

[0354] Except having changed the amine imide compound A into the amine imide composition S2, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0355] [Example 30]

[0356] Except having changed the amine imide compound A into the amine imide composition S2, the epoxy resin composition was prepared similarly to Example 2, and the curability and storage stability at room temperature were evaluated.

[0357] [Example 31]

[0358] Except having changed the amine imide compound A into the amine imide composition S3, the epoxy resin composition was prepared similarly to Example 2, and the curability and storage stability at room temperature were evaluated.

[0359] [Example 59]

[0360] Except having changed the amine imide compound A into the amine imide compound I, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0361] [Example 60]

[0362] Except having changed the amine imide compound A into the amine imide compound J, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0363] [Example 61]

[0364] Except having changed the amine imide compound A into the amine imide compound K, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0365] [Comparative Example 1]

[0366] An epoxy resin composition was prepared in the same manner as in Example 1 except that the amine imide compound A was changed to DBU ("diazabicycloundecene" manufactured by Tokyo Chemical Industry Co., Ltd.), and the curability and storage stability at room temperature were evaluated.

[0367] [Comparative Example 2]

[0368] Except having changed the amine imide compound A into DBU-phenolate ("U-CAT SA1" manufactured by SUN-PRO), the epoxy resin composition was prepared in the same manner as in Example 1, and the curability and storage stability at room temperature were evaluated.

[0369] [Comparative Example 3]

[0370] Except having changed the amine imide compound A into the acrylate-imidazole adduct, the epoxy resin composition was prepared similarly to Example 1, and the curability and storage stability at room temperature were evaluated.

[0371] The evaluation results of Examples 1 to 31, 59 to 61, and Comparative Examples 1 to 3 are shown in Tables 2 to 6.

[0372] [Table 2]

[0373]

[0374] [Table 3]

[0375]

[0376] [Table 4]

[0377]

[0378] [Table 5]

[0379]

[0380] [Table 6]

[0381]

[0382] [Preparation of epoxy resin composition (2)]

[0383] The epoxy resin compositions prepared in the following examples and comparative examples used the following epoxy resins and acid anhydrides as raw materials.

[0384] Epoxy resin: "BE-186EL" from Chang Chun Plastics Co., Ltd.

[0385] Acid anhydride: "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

[0386] When various raw materials were mixed, they were added so that the equivalent ratio of the epoxy group in the epoxy resin to the acid anhydride group in the acid anhydride became acid anhydride group / epoxy group=1.00.

[0387] Furthermore, each raw material was added in the amount shown in Tables 7 to 9 relative to 100 parts by mass of the epoxy resin.

[0388] An epoxy resin, an amine imide compound, an amine imide composition, DBU, U-CAT SA1, or an acrylate-imidazole adduct (hereinafter sometimes referred to as an amine imide compound, etc.) are placed in a plastic stirring container. These are stirred and mixed using a rotary / orbital stirrer ("ARE-310" manufactured by THINKY Corporation) to premix the epoxy resin and the amine imide compound, etc. Subsequently, a predetermined amount of acid anhydride is added to the premix, and further stirred and mixed to prepare an epoxy resin composition.

[0389] [Evaluation method of curability (2)]

[0390] As a method for evaluating curability (2), the prepared epoxy resin composition was heated and evaluated under the following conditions. Regarding the temperature at which 100 Pa·s was reached, a temperature below +15°C compared to the case where DBU was used as a curing accelerator was evaluated as "◎", a temperature between +15°C and below +30°C was evaluated as "○", a temperature between +30°C and below +45°C was evaluated as "△", and a temperature above +45°C was evaluated as "×".

[0391] <Measurement Conditions>

[0392] · Apparatus: Viscoelasticity measuring apparatus ("HAAKE MARS" manufactured by Thermo Scientific)

[0393] Sample mass: about 0.5mL

[0394] Plate shape: parallel

[0395] ·Measurement mode: constant shear rate (dγ / dt=1.0s -1 )

[0396] ·Measurement temperature: 40℃~240℃

[0397] Heating rate: 5℃ / min

[0398] [Evaluation method for storage stability (2)]

[0399] As a storage stability evaluation method (2), the viscosity of the epoxy resin composition at 25°C immediately after preparation was denoted as "η1", and the viscosity of the epoxy resin composition at 25°C after storage in a thermostatic chamber at 25°C for 3 days was denoted as "η2". The value calculated by η2 / η1 was determined as the viscosity increase ratio. A viscosity increase ratio of less than 3.0 times was evaluated as "◎", a viscosity increase ratio of 3.0 times or more and less than 7.0 times was evaluated as "○", a viscosity increase ratio of 7.0 times or more and less than 10.0 times was evaluated as "△", and a viscosity increase ratio of 10.0 times or more was evaluated as "×".

[0400] [Evaluation method for prepreg surface smoothness]

[0401] The prepared epoxy resin composition was coated on a carbon fiber cloth ("TORAYCA CLOTH CO6343" manufactured by Toray Industries, Ltd.) (weight per unit area: 198 g / m 2 ) for 5 minutes and then heated in a 170°C oven for 10 minutes to produce a prepreg. The surface condition of the resulting prepreg was then observed. A smooth surface was rated "○," while a surface with irregularities due to pores or the like was rated "×."

[0402] [Evaluation method of prepreg adhesion]

[0403] The prepared epoxy resin composition was coated on a carbon fiber cloth ("TORAYCA CLOTH CO6343" manufactured by Toray Industries, Ltd.) (weight per unit area: 198 g / m 2 ) for 5 minutes and heated in a 170°C oven for 10 minutes to produce a prepreg. The tackiness of the resulting prepreg was checked. If not tacky, it was rated "○"; if tacky, it was rated "×".

[0404] [Evaluation method of permeability]

[0405] A carbon fiber cloth ("TORAYCA CLOTHCO6343" manufactured by Toray Industries, Ltd.) (weight per unit area: 198 g / m2) was placed between the pressure filters as filter cloth. 2 ), the prepared epoxy resin composition was pressure-filtered at room temperature using 0.2 L / min nitrogen. 10 mg of the epoxy resin composition obtained as the filtrate was placed in the aluminum container of a differential scanning calorimeter (DSC220C, manufactured by SII Corporation). The mixture was heated in an oven at 180°C for 1.5 hours, then quenched. The reaction rate was calculated based on the change in DSC heat release before and after filtration. A reaction rate of 95% or higher was rated as "○," while a reaction rate of less than 95% was rated as "×."

[0406] It should be noted that in this evaluation, when an amine imide compound or the like is used as a curing accelerator, if the curing accelerator has excellent permeability, there is no difference in the amount of curing accelerator in the epoxy resin composition before and after pressure filtration, confirming that the desired reactivity can be achieved. On the other hand, if the curing accelerator has poor permeability, at least a portion of the curing accelerator is trapped by the carbon fiber cloth, resulting in a decrease in the amount of curing accelerator in the epoxy resin composition after pressure filtration, confirming that the desired reactivity cannot be achieved.

[0407] [Example 32]

[0408] 20 g of an epoxy resin ("BE-186EL" manufactured by Chang Chun Plastics Co., Ltd.) and 0.6 g of an amine imide compound A were placed in a plastic stirring container and stirred and mixed using a rotary / revolving stirrer ("ARE-310" manufactured by THINKY). Subsequently, 17.9 g of an acid anhydride ("HN-5500" manufactured by Hitachi Chemical Co., Ltd.) was added and further stirred and mixed to prepare an epoxy resin composition. The curability was evaluated using the curability evaluation method (2) described above, and the storage stability at room temperature was evaluated using the storage stability evaluation method (2) described above. Furthermore, the prepreg surface smoothness, prepreg tack, and permeability were also evaluated.

[0409] [Example 33]

[0410] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amount of amine imide compound A added was changed to 3.6 g, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0411] [Example 34]

[0412] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound B, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0413] [Example 35]

[0414] Except that amine imide compound A was changed to amine imide compound B and the addition amount of amine imide compound B was changed to 3.6 g, an epoxy resin composition was prepared in the same manner as in Example 32, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0415] [Example 36]

[0416] Except that amine imide compound A was changed to amine imide compound B and the addition amount of amine imide compound B was changed to 4.8 g, an epoxy resin composition was prepared in the same manner as in Example 32, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0417] [Example 37]

[0418] Except that amine imide compound A was changed to amine imide compound C and the addition amount of amine imide compound C was changed to 0.2 g, an epoxy resin composition was prepared in the same manner as in Example 32, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0419] [Example 38]

[0420] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound C, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0421] [Example 39]

[0422] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound D, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0423] [Example 40]

[0424] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound E, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0425] [Example 41]

[0426] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound F, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0427] [Example 42]

[0428] Except that amine imide compound A was changed to amine imide compound F and the addition amount of amine imide compound F was changed to 2.0 g, an epoxy resin composition was prepared in the same manner as in Example 32, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0429] [Example 43]

[0430] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound G, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0431] [Example 44]

[0432] Except that amine imide compound A was changed to amine imide compound H and the addition amount of amine imide compound H was changed to 0.2 g, an epoxy resin composition was prepared in the same manner as in Example 32, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0433] [Example 45]

[0434] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound H, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0435] [Example 46]

[0436] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound L, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0437] [Example 47]

[0438] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound M, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0439] [Example 48]

[0440] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound N, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0441] [Example 49]

[0442] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound O, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0443] [Example 50]

[0444] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide composition O2, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0445] [Example 51]

[0446] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide composition O3, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0447] [Example 52]

[0448] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound P, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0449] [Example 53]

[0450] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound Q, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0451] [Example 54]

[0452] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide composition Q2, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0453] [Example 55]

[0454] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound R, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0455] [Example 56]

[0456] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound S, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0457] [Example 57]

[0458] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide composition S2, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0459] [Example 58]

[0460] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide composition S3, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0461] [Example 62]

[0462] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound I, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0463] [Example 63]

[0464] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound J, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0465] [Example 64]

[0466] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the amine imide compound K, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0467] [Comparative Example 4]

[0468] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was replaced with DBU ("diazabicycloundecene" manufactured by Tokyo Chemical Industry Co., Ltd.), and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0469] [Comparative Example 5]

[0470] An epoxy resin composition was prepared in the same manner as in Example 32 except that amine imide compound A was changed to DBU-phenolate ("U-CAT SA1" manufactured by SUN-PRO). The curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0471] [Comparative Example 6]

[0472] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to the acrylate-imidazole adduct A, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tack, and permeability were evaluated.

[0473] [Comparative Example 7]

[0474] Except that the amine imide compound A was changed to a powdered amine curing agent ("AMICURE PN-23" manufactured by Ajinomoto Fine Science Co., Ltd.), an epoxy resin composition was prepared in the same manner as in Example 32, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0475] The evaluation results of Examples 32 to 58, 62 to 64, and Comparative Examples 4 to 7 are shown in Tables 7 to 9.

[0476] [Table 7]

[0477]

[0478] [Table 8]

[0479]

[0480] [Table 9]

[0481]

[0482] From the results in Tables 1 to 9, it was confirmed that the epoxy resin compositions of Examples 1 to 64 obtained using the amine imide compounds or amine imide compositions A to S3 obtained in Synthesis Examples 1 to 24 were excellent in curability and storage stability.

[0483] Furthermore, the results in Tables 7 to 9 confirm that the epoxy resin compositions of Examples 32 to 64 obtained using the amine imide compounds or amine imide compositions A to S3 obtained in Production Examples 1 to 24 also have excellent permeability and exhibit good prepreg properties.

[0484] On the other hand, it was confirmed that the epoxy resin compositions of Comparative Examples 1 to 7 were excellent in curability, but were poor in storage stability at room temperature.

[0485] [Measurement method of shear bond strength]

[0486] The tensile shear bond strength with respect to the steel plate was measured in accordance with JIS K6850.

[0487] The shear adhesion evaluation was performed using the epoxy resin compositions of Examples 65 to 68 prepared as follows.

[0488] [Examples 65 to 76]

[0489] As epoxy resins used in the epoxy resin composition, bisphenol A type epoxy resin: "BE-186EL" manufactured by Chang Chun Plastics Co., Ltd., bisphenol F type epoxy resin: "jER806" manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin: glycidylamine-based epoxy resin "jER630" manufactured by Mitsubishi Chemical Corporation, and naphthalene type epoxy resin: "HP-4032D" manufactured by DIC Corporation were used.

[0490] The specified amine imide compound shown in Table 10 below was added to 20 parts by mass relative to 100 parts by mass of the total epoxy resin. Acrylate-imidazole was added to 10 parts by mass. The epoxy resin and amine imide compound were placed in a plastic stirring container and stirred and mixed using a rotary / revolving stirrer ("ARE-310" manufactured by THINKY) to prepare an epoxy resin composition.

[0491] The epoxy resin composition prepared as described above was applied between two steel plate test pieces (SPCC-SB, manufactured by Standard-Testpiece Co., Ltd.) at a bonding area of ​​12.5 mm x 5 mm. The composition was then heated in a heating furnace at a set temperature of 150°C for 2 hours to thermally cure and bond the two pieces together. The tensile shear bond strength of the resulting test pieces was measured using an Autograph AGS-X 5kN (manufactured by Shimadzu Corporation) in a constant temperature and humidity chamber at 23°C and 50% RH. The median value of the obtained values ​​was used as the tensile shear bond strength to the steel plate substrate.

[0492] [Table 10]

[0493]

[0494] According to the measurement results shown in Table 10, it can be seen that -NN- has substantially the same decomposition temperature (starting temperature, peak temperature) as -NN- and -N - -N + Compared with a substance with one, a molecule has multiple -N - -N + The shear bonding strength of the structure (amine imide compounds O, M, etc.) under the same curing conditions becomes higher. The reason for this is that there are multiple -N - -N + -, the active ingredients in the curing agent mass increase.

[0495] This application is based on Japanese Patent Application No. 2020-121122 filed with the Japan Patent Office on July 15, 2020, the contents of which are incorporated herein by reference.

[0496] Industrial applicability

[0497] The amine imide compound and epoxy resin composition of the present invention have industrial applicability as sealing materials, adhesives, printed circuit board materials, coatings, composite materials, semiconductor sealing materials such as underfill and molding, conductive adhesives such as ACF, printed wiring boards such as solder masks and cover films, and composite materials such as prepregs impregnated with glass fibers or carbon fibers.

Claims

1. An amine imide compound represented by the following formula (1), (2) or (3), In formulas (1) to (2), R1 each independently represents a hydrogen atom, or a monovalent organic group or an n-valent organic group optionally containing a hydroxyl group, a carbonyl group, an ester bond, or an ether bond and having 1 to 15 carbon atoms; R2 and R3 each independently represent a heterocyclic ring having 7 or less carbon atoms formed by linking R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group optionally containing an oxygen atom; n represents an integer from 1 to 3, In formula (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or an n-valent organic group optionally having a hydroxyl group, a carbonyl group, an ester bond or an ether bond and having 1 to 15 carbon atoms; R2 and R3 each independently represent an alkyl group, an aryl group, an arylalkyl group, an unsubstituted or substituted group, having 1 to 12 carbon atoms, or a heterocycle having 7 or less carbon atoms formed by connecting R2 and R3; R4 each independently represents a hydrogen atom, or an n-valent organic group optionally containing an oxygen atom; and n represents an integer from 1 to 3.

2. The amine imide compound according to claim 1, wherein In formulae (1) to (3), when R4 is an organic group, the number of carbon atoms of R4 is 1 to 30.

3. The amine imide compound according to claim 2, which is represented by the following formula (1) or (2): In formulas (1) to (2), R1 each independently represents a hydrogen atom, or a monovalent organic group or an n-valent organic group optionally having a hydroxyl group, a carbonyl group, an ester bond, or an ether bond and having 1 to 15 carbon atoms; R2 and R3 each independently represent a heterocycle having 7 or less carbon atoms formed by linking R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group optionally containing an oxygen atom and having 1 to 30 carbon atoms; and n represents an integer from 1 to 3.

4. The amine imide compound according to any one of claims 1 to 3, wherein The R1 in the formula (1) or (3) is a group represented by the following formula (4) or (5), In formula (4) and (5), R 11 Each independently represents an aryl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 9 carbon atoms; and n each independently represents an integer of 0 to 6.

5. The amine imide compound according to claim 4, wherein In formula (5), n is 0 or 1.

6. The amine imide compound according to any one of claims 1 to 3, wherein The R1 in the formula (2) is a group represented by the following formula (6) or (7), In formula (6) and (7), R 12 and R 13 Each independently represents a single bond, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms.

7. The amine imide compound according to claim 6, wherein In formula (7), R 13 is a single bond or a methyl group.

8. The amine imide compound according to claim 1 or 2, wherein At least one of R2 and R3 in formula (3) represents an aralkyl group.

9. The amine imide compound according to any one of claims 1 to 3, wherein The heterocyclic ring having 7 or less carbon atoms formed by connecting R2 and R3 is represented by the following formula (8): 23 With N in formula (1), (2) or (3) + The heterocyclic ring formed In formula (8), R 23 Indicates that N + Groups that together form a heterocyclic structure.

10. The amine imide compound according to any one of claims 1 to 3, wherein The heterocyclic ring having 5 carbon atoms formed by connecting R2 and R3 is represented by the following formula (8): 23 With N in formula (1), (2) or (3) + The heterocyclic ring formed In formula (8), R 23 Indicates that N + Groups that together form a heterocyclic structure.

11. The amine imide compound according to any one of claims 1 to 3, wherein The R4 in the formula (1) or (2) is a linear or branched alkyl group having 3 to 12 carbon atoms, or a linear or branched alkenyl group having 3 to 6 carbon atoms.

12. The amine imide compound according to claim 1, wherein The R4 in the formula (3) is a group represented by the following formula (9) or (10), In formulas (9) and (10), R 41 and R 42 Each independently represents an alkyl group, an aryl group, or an aralkyl group having 1 to 5 carbon atoms; and each independently represents an integer of 0 to 10.

13. The amine imide compound according to any one of claims 1 to 3, wherein The amine imide compound is represented by the formula (2) or (3), where n is 2 or 3.

14. The amine imide compound according to any one of claims 1 to 3, wherein The amine imide compound is represented by the formula (2) or (3), and n is 2. 15 . The amine imide compound according to claim 1 , having a viscosity at 25° C. of 1300 Pa·s or less. The amine imide compound according to claim 15 , which has a viscosity at 25° C. of 900 Pa·s or less. The amine imide compound according to claim 15 , which has a viscosity at 25° C. of 800 Pa·s or less. The amine imide compound according to claim 15 , which has a viscosity at 25° C. of 700 Pa·s or less.

19. The amine imide compound according to any one of claims 1 to 3, wherein the peak temperature T of the exothermic peak associated with the decomposition of the N-N bond in differential thermal analysis is peak With the starting temperature T onset Difference T peak -T onset Below 45°C.

20. The amine imide compound according to claim 19, wherein the peak temperature T of the exothermic peak associated with the decomposition of the N-N bond in differential thermal analysis is peak With the starting temperature T onset Difference T peak -T onset 5°C or higher and 40°C or lower.

21. The amine imide compound according to claim 19, wherein the peak temperature T of the exothermic peak associated with the decomposition of the N-N bond in differential thermal analysis is peak With the starting temperature T onset Difference T peak -T onset 10°C or higher and 35°C or lower.

22. The amine imide compound according to claim 19, wherein the peak temperature T of the exothermic peak associated with the decomposition of the N-N bond in differential thermal analysis is peak With the starting temperature T onset Difference T peak -T onset 15°C or higher and 30°C or lower.

23. The amine imide compound according to claim 19, wherein The T peak is 100°C or higher and 250°C or lower, the T onset It is 80°C or higher and 200°C or lower.

24. The amine imide compound according to claim 19, wherein The T peak is 100°C or higher and 220°C or lower, the T onset It is 80°C or higher and 185°C or lower.

25. The amine imide compound according to claim 19, wherein The T peak is 100°C or higher and 200°C or lower, the T onset It is 80°C or higher and 170°C or lower.

26. The amine imide compound according to claim 19, wherein The T peak is 100°C or higher and 180°C or lower, the T onset It is 80°C or higher and 160°C or lower.

27. An amine imide composition comprising a plurality of the amine imide compounds according to any one of claims 1 to 26.

28. An amine imide composition comprising an amine imide compound represented by the following formula (1) and the following formula (3), In formula (1), R1 each independently represents a hydrogen atom, or a monovalent organic group or an n-valent organic group optionally containing a hydroxyl group, a carbonyl group, an ester bond, or an ether bond and having 1 to 15 carbon atoms; R2 and R3 each independently represent a heterocyclic ring having 7 or less carbon atoms formed by linking R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group optionally containing an oxygen atom and having 1 to 30 carbon atoms; n represents an integer from 1 to 3, In formula (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group optionally having a hydroxyl group, a carbonyl group, an ester bond or an ether bond and having 1 to 15 carbon atoms; R2 and R3 each independently represent an alkyl group, an aryl group, an arylalkyl group, which is unsubstituted or has a substituent and has 1 to 12 carbon atoms, or a heterocycle with 7 or less carbon atoms formed by connecting R2 and R3; R4 each independently represents a hydrogen atom, or an n-valent organic group optionally containing an oxygen atom and having 1 to 30 carbon atoms; and n represents an integer from 1 to 3.

29. A curing agent comprising the amine imide compound according to any one of claims 1 to 26, or the amine imide composition according to claim 27 or 28. 30 . An epoxy resin composition comprising an epoxy resin (α) and the curing agent (β) according to claim 29 .

31. The epoxy resin composition according to claim 30, wherein The content of the curing agent (β) is 1 to 50 parts by mass based on 100 parts by mass of the epoxy resin (α).

32. The epoxy resin composition according to claim 31, wherein The content of the curing agent (β) is 1 to 30 parts by mass based on 100 parts by mass of the epoxy resin (α).

33. The epoxy resin composition according to claim 31, wherein The content of the curing agent (β) is 2 to 20 parts by mass based on 100 parts by mass of the epoxy resin (α). 34 . The epoxy resin composition according to claim 30 , further comprising an acid anhydride curing agent (γ).

35. A method for producing an amine imide compound, the method comprising producing the amine imide compound according to any one of claims 1 to 26, or the amine imide compound in the amine imide composition according to claim 27 or 28. The method comprises a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B), and a glycidyl ether compound (C). 36 . A sealing material, which is a cured product of the epoxy resin composition according to claim 30 .

37. An adhesive comprising the epoxy resin composition according to any one of claims 30 to 34, The curing agent (β) includes an amine imide compound represented by the formula (3).

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