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

Abstract

Provided is an amine imide compound having excellent permeability and excellent curability and storage stability. An amine imide compound represented by the following formula (1), (2) or (3). (In formulas (1) to (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or an n-valent organic group having 1 to 15 carbon atoms and optionally having a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R2 and R3 each independently represent an alkyl group, an aryl group, an aralkyl group having 1 to 12 carbon atoms, which is unsubstituted or has a substituent, or a heterocyclic ring having 7 or less carbon atoms formed by connecting R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group or an n-valent organic group having 1 to 30 carbon atoms and optionally containing an oxygen atom; n represents an integer from 1 to 3.)

Description

Technical Field

[0001] 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

[0002] Epoxy resins have been used in a wide range of applications, including coatings, electrical and electronic insulation materials, and adhesives, because their cured products have excellent properties in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesion.

[0003] The epoxy resin composition generally used today is a so-called two-component epoxy resin composition in which two liquids, an epoxy resin and a curing agent, are mixed when used.

[0004] Two-component epoxy resin compositions can cure at room temperature, but on the other hand, the epoxy resin and curing agent need to be stored separately and measured and mixed according to the usage. Therefore, storage and operation are relatively complicated. Furthermore, the usable time is limited, so there is a problem that large quantities cannot be mixed in advance.

[0005] In order 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). For example, an epoxy resin composition obtained by blending a latent curing agent with an epoxy resin can be mentioned.

[0006] In addition, the requirements for today's electronic equipment are divided into multiple branches such as miniaturization, high functionality, light weight, high functionality, and multifunctionality. For example, in the mounting technology of semiconductor chips, further miniaturization, miniaturization, and high density are also required by fine pitch between electrode pads. Therefore, in the bottom fill as an adhesive used in the gap between the chip and the substrate, it is required to penetrate into a narrower gap.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent No. 6282515

[0010] Patent Document 2: Japanese Patent Application Publication No. 2003-96061

[0011] Patent Document 3: Japanese Patent Application Publication No. 2000-229927 Summary of the invention

[0012] Problem that the invention aims to solve

[0013] Latent curing agents that constitute one-component epoxy resin compositions are required to have both good curing properties and storage stability after mixing with the epoxy resin, and further, good permeability into narrow gaps in electronic components and between dense fibers such as carbon fibers and glass fibers. However, latent curing agents that meet these properties have not yet been obtained.

[0014] For example, Patent Document 1 discloses, as a curing agent, a liquid bisimidazole compound obtained by modifying imidazole with acrylate, but this has the problem that there is room for improvement in terms of storage stability.

[0015] In addition, 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.

[0016] 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.

[0017] Therefore, in view of the above-mentioned problems of the prior art, an object of the present invention is to provide an amine imide compound having excellent permeability and excellent curability and storage stability.

[0018] Solutions for solving problems

[0019] As a result of intensive studies, the present inventors have found that an amine imide compound of a specific structure is excellent in permeability, curability, and storage stability, thereby completing the present invention.

[0020] That is, the present invention is as follows.

[0021] [1] An amine imide compound represented by the following formula (1), (2) or (3).

[0022]

[0023] (In formulae (1) to (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group which optionally has a hydroxyl group, a carbonyl group, an ester bond or an ether bond and has 1 to 15 carbon atoms; R2 and R3 each independently represent an alkyl group, an aryl group, an aralkyl group which is unsubstituted or has a substituent and has 1 to 12 carbon atoms, or a heterocyclic ring having 7 or less carbon atoms formed by connecting R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group which optionally contains an oxygen atom and has 1 to 30 carbon atoms; and n represents an integer from 1 to 3.)

[0024] [2] The amine imide compound according to [1] above, wherein the R1 in the formula (1) or (3) above is a group represented by the following formula (4) or (5).

[0025]

[0026] (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 of 0 to 6.

[0027] [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).

[0028]

[0029] (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.)

[0030] [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.

[0031] [5] The amine imide compound according to any one of [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), wherein R 23 and N in formula (1), (2) or (3) + The formed heterocycle.

[0032]

[0033] (In formula (8), R 23 Indicates that N + Groups that together form a heterocyclic structure.

[0034] [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.

[0035] [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).

[0036]

[0037] (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 of 0 to 10.

[0038] [8] 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 or 3.

[0039] [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.

[0040]

[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.

[0041]

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

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

[0042]

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

[11] above.

[0043]

[13] The amine imide composition according to

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

[0044]

[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.

[0045]

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

[14] above.

[0046]

[16] The epoxy resin composition according to

[15] above, 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).

[0047]

[17] The epoxy resin composition according to

[15] or

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

[0048]

[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,

[0049] The method comprises a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B) and a glycidyl ether compound (C).

[0050]

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

[15] to

[17] .

[0051]

[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).

[0052] Effects of the Invention

[0053] According to the present invention, a latent curing agent having excellent permeability, excellent curability and excellent storage stability can be provided. DETAILED DESCRIPTION

[0054] Hereinafter, a method for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. This embodiment is an example for explaining 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 scope of its purpose.

[0055] 〔Amine imide compounds〕

[0056] The amine imide compound of the present embodiment is represented by the following formula (1), (2) or (3).

[0057]

[0058] (In formulae (1) to (3), R1 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group which optionally has a hydroxyl group, a carbonyl group, an ester bond or an ether bond and has 1 to 15 carbon atoms; R2 and R3 each independently represent an alkyl group, an aryl group, an aralkyl group which is unsubstituted or has a substituent and has 1 to 12 carbon atoms, or a heterocyclic ring having 7 or less carbon atoms formed by connecting R2 and R3; R4 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group which optionally contains an oxygen atom and has 1 to 30 carbon atoms; and n represents an integer from 1 to 3.)

[0059] The amine imide compound of the present embodiment does not have a substituent with curing properties in the state of the amine imide compound, so even if it is compatible with the epoxy resin at room temperature, it will not undergo an addition reaction with the epoxy group. However, as shown in the following reaction formula, heating causes the NN bond to cleave, generating acyl nitrene and tertiary amine. Furthermore, the acyl nitrene 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. That is, the amine imide compound of the present embodiment functions as a latent curing agent.

[0060]

[0061] In addition, the amine imide compound of the present embodiment has a hydroxyl group, and therefore, as shown in the following reaction formula, the isocyanate generated by heating undergoes an addition reaction with the tertiary amine to convert into a structure having a tertiary amine and a carbamate bond in one molecule. This structure has a curing property superior to that of isocyanate and tertiary amine, and therefore, the amine imide compound of the present embodiment functions as a latent curing agent having excellent curing property.

[0062]

[0063] It should be noted that the compound represented by formula (2) is a compound in which the compound represented by formula (1) is connected 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 connected 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, and in the case of the compound represented by formula (3), a monovalent isocyanate compound and an n-valent tertiary amine are generated by heating.

[0064] The decomposition temperature of the NN bond of the amine imide compound of the present embodiment is the peak temperature (T peak ) is preferably 100°C to 250°C, more preferably 100°C to 220°C, further preferably 100°C to 200°C, and still further preferably 100°C to 180°C.

[0065] 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. It should be noted that the top temperature (T 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.

[0066] In addition, the starting point temperature (T onset ) is preferably 80°C to 200°C, more preferably 80°C to 185°C, further preferably 80°C to 170°C, and still further preferably 80°C to 160°C.

[0067] By making T onset When the temperature is 80°C or higher, the storage stability tends to be further improved. onset When the temperature is 200°C or lower, the curing performance of the amine imide compound tends to be further improved. It should be noted that the starting point temperature (T 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 ).

[0068] The aforementioned vertex temperature (T peak ) and the aforementioned starting temperature (T onset ) difference (T peak -T onset ) is preferably 45°C or less, more preferably 40°C or less, further preferably 35°C or less, and further preferably 30°C or less. peak -T onset ) is 45°C or less, so that the decomposition of the N-N bond by heating proceeds rapidly, and the sharpness 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 further preferably 15°C or higher.

[0069] Vertex 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 the present embodiment. For example, there is a tendency that R1 contributes to the low energy of the cleavage of the N-N bond, and R2 and R3 contribute to the low energy of the cleavage reaction caused by the instability caused by stereo steric hindrance. Therefore, as R1, R2 and R3 described later, by appropriately combining groups that contribute to improving the curing performance and other groups, their temperatures can be controlled.

[0070] The amine imide compound of the present embodiment is preferably a compound that is liquid at room temperature.

[0071] In this embodiment, the viscosity at 25° C. can be used as an index indicating that the compound is 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 further preferably 700 Pa·s or less.

[0072] In addition, the lower limit of the viscosity at 25° C. is not particularly limited, but is preferably 0.01 Pa·s or more.

[0073] The amine imide compound of the present 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 and the like are further improved.

[0074] 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).

[0075] It is believed that R1 in formula (1), (2) or (3) contributes to the low energy of cleavage of the N-N bond, R2 and R3 contribute to the low energy of the cleavage reaction caused by the instability due to stereo steric hindrance, and R4 contributes to the liquidization of the compound and the suppression of the decrease in the glass transition temperature of the obtained cured product, but there is no particular limitation. The details of each group are described below.

[0076] In formulae (1), (2) and (3), R1 independently represents a hydrogen atom, or a monovalent organic group or an nvalent organic group which optionally has a hydroxyl group, a carbonyl group, an ester bond or an ether bond and has 1 to 15 carbon atoms. Such an organic group is not particularly limited, and examples thereof include a hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted with a hydroxyl group or a carbonyl group, or a group in which a part of the carbon atoms constituting the hydrocarbon group is replaced with an ester bond or an ether bond. Examples of such a hydrocarbon group include a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an ethylhexyl group, and the like; an alkenyl group such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, a decenyl group, a dodecenyl group, a hexadecenyl group, an octadecenyl group, and the like; an aryl group such as a phenyl group; or an aralkyl group formed by a combination of an alkyl group and a phenyl group such as a methylphenyl group, an ethylphenyl group, and a propylphenyl group.

[0077] 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, sulfone groups, nitro groups, hydroxyl groups, acyl groups, and aldehyde groups.

[0078] The number of carbon atoms of the organic group represented by R1 is 1 to 15, preferably 1 to 12, and more preferably 1 to 7. When the number of carbon atoms of the organic group represented by R1 is within the above range, 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. In addition, when the number of carbon atoms of the organic group represented by R1 is within the above range, the ease of obtaining the raw material is further improved.

[0079] 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.

[0080]

[0081] (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 of 0 to 6.

[0082] Among the above, the group in which n in formula (5) 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. Such a diketone structure tends to further improve the curing performance of the amine imide compound.

[0083] 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.

[0084] 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 is easily obtained, and the curing performance of the amine imide compound is further improved.

[0085]

[0086] (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.)

[0087] Among the above, R in formula (7) is preferably 13is 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.

[0088] 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.

[0089] The alkyl group having 1 to 12 carbon atoms represented by R2 or R3 is not particularly limited, and examples thereof include straight-chain alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched-chain 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. In addition, the above-mentioned alkyl group may be a group obtained by combining a straight-chain alkyl group or a branched-chain alkyl group with a cyclic alkyl group. Furthermore, the above-mentioned alkyl group may contain an unsaturated linking group.

[0090] The number of carbon atoms of 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 in which the alkyl group of the asymmetric dialkylhydrazine has a small number of carbon atoms are toxic to the human body in addition to the danger of explosion, etc. By setting the number of carbon atoms of the alkyl group represented by R2 or R3 to 2 or more, it is possible to avoid using raw materials with such toxic risks. In addition, by setting the number of carbon atoms of the alkyl group represented by R2 or R3 to 5 or more, 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.

[0091] 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, and more preferably a methylphenyl (benzyl) group. As a result, there is a tendency that the curing performance of the amine imide compound is 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.

[0092] 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 azido group, a thiol group, a sulfone group, a nitro group, a hydroxyl group, an acyl group and an aldehyde group.

[0093] 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.

[0094]

[0095] (In formula (8), R 23 Indicates that N + Groups that together form a heterocyclic structure.

[0096] 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, thiazine ring; six-membered rings such as piperidine ring; and seven-membered rings such as hexamethyleneimine ring and azepine ring.

[0097] Among them, as the heterocyclic ring, preferably a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, an azepine ring, and more preferably a six-membered ring and a seven-membered ring. 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.

[0098] In addition, the substituent is not particularly limited, and examples thereof include an alkyl group, an aryl group, or a substituent in the above 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.

[0099] In formulae (1), (2) and (3), R4 represents a hydrogen atom, or a monovalent organic group or an nvalent organic group which optionally contains an oxygen atom and has 1 to 30 carbon atoms. Such an organic group is not particularly limited, and examples thereof include a hydrocarbon group; a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is replaced by a hydroxyl group, a carbonyl group or a group containing a silicon atom; or a group in which a part of the carbon atoms constituting the hydrocarbon group is replaced by an ester bond, an ether bond or a silicon atom. Examples of such a hydrocarbon group include a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and an ethylhexyl group; an alkenyl group such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, an octenyl group, a decenyl group, a dodecenyl group, a hexadecenyl group and an octadecenyl group; an aryl group such as a phenyl group; or an aralkyl group formed by a combination of an alkyl group and a phenyl group such as a methylphenyl group, an ethylphenyl group and a propylphenyl group.

[0100] The hydrocarbon group represented by R4 includes bisphenol skeletons such as bisphenol A skeleton, bisphenol AP skeleton, bisphenol B skeleton, bisphenol C skeleton, bisphenol E skeleton, and bisphenol F skeleton. The organic group including the bisphenol skeleton is not particularly limited, and examples thereof include groups in which a polyoxyalkylene group is added to the hydroxyl group of each bisphenol skeleton.

[0101] 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, there is a tendency to obtain a liquid amine imide compound that satisfies the above-mentioned viscosity, and the curing properties of the amine imide compound are further improved. In addition, there is a tendency that Tg further improves in the cured product obtained using the amine imide compound.

[0102] As described above, the carbon number of the organic group represented by R4 is 1 to 30, preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 8. By making the carbon number of the organic group represented by R4 within the above range, 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. In addition, the Tg of the cured product obtained using the amine imide compound is further improved, and further, by making the carbon number of the organic group represented by R4 within the above range, the ease of obtaining the raw material is further improved.

[0103] 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. 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.

[0104] In addition, R4 in formula (3) is preferably a group represented by the following formula (9) or (10). By having such a group, 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.

[0105]

[0106] (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 of 0 to 10.

[0107] The amine imide compound of the present embodiment is represented by the above formula (2) or (3), and n in the formula (2) or (3) is preferably 2 or 3, and more preferably 2. This can provide an effect of improving curability.

[0108] [Amine imide composition]

[0109] The amine imide composition of the present embodiment comprises the amine imide compounds shown in multiple 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 characteristics, the amine imide composition is set to comprise multiple amine imide compounds of the present embodiment. It should be noted that multiple amine imide compounds represented by the same formula but with different structures may be included.

[0110] In particular, from the viewpoint of controlling the viscosity, an amine imide composition containing the amine imide compounds represented by the above formula (1) and formula (3) is preferred.

[0111] When a plurality of amine imide compounds are contained, the viscosity tends to be easily controlled by containing 0.1% by mass to 99.5% by mass of the amine imide compound represented by the above formula (1).

[0112] In the case of an amine imide composition containing a plurality of amine imide compounds, the amine imide composition may be obtained by mixing the plurality of amine imide compounds, or may be obtained by simultaneously producing the plurality of amine imide compounds in the method for producing the amine imide compound described below.

[0113] [Method for producing amine imide compound and amine imide composition]

[0114] 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 structure.

[0115] 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.

[0116] 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).

[0117] Hereinafter, the manufacturing method will be described.

[0118] The carboxylate compound (A) is not particularly limited, and examples thereof include monocarboxylate compounds and dicarboxylate compounds.

[0119] As the specific example of the monocarboxylic acid ester compound, methyl lactate, ethyl lactate, methyl phenethylate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl enanthate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonic acid, methyl benzoylformate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-tert-butoxybenzoylmethyl etc. can be listed. In addition, ethyl esters, propyl esters etc. can also be used instead of them. 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 azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetone dicarboxylate, and diethyl 1,3-acetone dicarboxylate. In addition, diethyl esters, dipropyl esters, etc. may be used instead of these.

[0120] Among these, ethyl lactate, methyl mandelic acid, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonic acid, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartaric acid, 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.

[0121] 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.

[0122] 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.

[0123] Among these, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine and 1-aminomorpholine are preferred from the viewpoint of curability and liquefaction. Furthermore, among these, dibenzylhydrazine and 1-aminopiperidine are more preferred from the viewpoint of easy availability and safety. The hydrazine compound (B) may be used alone or in combination of two or more.

[0124] 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 their condensation products; aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether, etc.

[0125] Among these, methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, tert-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.

[0126] Furthermore, among these, n-butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, trimethylolpropane polyglycidyl ether, ethylene oxide addition type bisphenol A type diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, and propylene oxide addition type bisphenol A type diglycidyl ether are more preferred from the viewpoint of easy availability and Tg of the cured product. The glycidyl ether compound (C) may be used alone or in combination of two or more.

[0127] The addition amount of the carboxylate compound (A), the hydrazine compound (B) and the glycidyl ether compound (C) in the reaction system can be expressed by the molar ratio of the functional groups. The carboxylate group of the carboxylate compound (A) is preferably 0.8 to 3.0 moles, more preferably 0.9 to 2.8 moles, and further preferably 0.95 to 2.5 moles relative to 1 mole of the primary amine of the hydrazine compound (B). In addition, the glycidyl group of the glycidyl ether compound (C) is preferably 0.8 to 2.0 moles, more preferably 0.9 to 1.5 moles, and further preferably 0.95 to 1.4 moles relative to 1 mole of the primary amine of the hydrazine compound (B).

[0128] 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.

[0129] In the method for producing the amine imide compound and the amine imide composition of the present embodiment, the reaction of the components (A) to (C) proceeds even without using a solvent, but it is preferred to use a solvent from the viewpoint of uniformly proceeding the reaction.

[0130] 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.

[0131] The reaction temperature is preferably 10 to 70° C., more preferably 20 to 60° C. When the reaction temperature is 10° C. or higher, the reaction proceeds quickly, and the purity of the obtained amine imide compound tends to be further improved. In addition, when the reaction temperature is 60° C. or lower, the polymerizing reaction of the glycidyl ether compounds (C) can be effectively suppressed, and therefore, the purity of the amine imide compound tends to be further improved.

[0132] The reaction time is preferably 1 to 7 days, more preferably 1 to 6 days, and even more preferably 1 to 4 days.

[0133] After the reaction is finished, the obtained reactant can be refined by known purification methods such as cleaning, extraction, recrystallization, column chromatography, etc. For example, after the reaction solution dissolved in the organic solvent is washed with water, the organic layer is heated under normal pressure or reduced pressure, so that unreacted raw materials and organic solvent can be removed from the reaction solution to reclaim the amine imide compound. Then, the obtained reactant can be refined by column chromatography to reclaim the amine imide compound.

[0134] 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.

[0135] 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.

[0136] The filler used in column chromatography can be alumina, silica gel and the like. The developing solvent can be ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol and the like alone or in combination.

[0137] 〔Curing agent〕

[0138] The curing agent of the present embodiment contains the amine imide compound or amine imide composition of the present embodiment described above.

[0139] The curing agent of the present embodiment may contain other components in addition to the amine imide compound or the amine imide composition.

[0140] 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 the present embodiment, the content thereof is preferably 90% by mass or less.

[0141] A preferred form of the amine imide compound of the present embodiment is liquid at room temperature, in which case, the amine imide compound has excellent compatibility with epoxy resins and can be suitably used as an epoxy resin composition to which other components are added.

[0142] 〔Epoxy resin composition〕

[0143] 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 as required, and optional components generally known to be used in epoxy resin compositions for various purposes.

[0144] 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. esters, diphenyl sulfoxide epoxy resins, diphenyl sulfone epoxy resins, diphenyl disulfide epoxy resins, naphthalene epoxy resins, anthracene epoxy resins, hydroquinone epoxy resins, methyl hydroquinone epoxy resins, dibutyl hydroquinone epoxy resins, resorcinol epoxy resins, methyl resorcinol epoxy resins, catechol epoxy resins, N,N-diglycidyl aniline epoxy resins, ethylene oxide addition type bisphenol A epoxy resins, propylene oxide addition 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 be used in combination.

[0145] The epoxy resin composition of the present embodiment may 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, diaminodiphenyl sulfone, diethylenetriamine, triethylenetetramine, isophoronediamine, polyalkylene glycol polyamine, polyamide resin synthesized from dimers 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 curing agents such as dicarboxylic anhydride; phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenolic resin, biphenyl modified phenol aralkyl resin, dicyclopentadiene modified phenolic resin, aminotriazine modified phenolic resin, naphthol novolac resin, naphthol-phenol co-condensation novolac resin, naphthol-cresol co-condensation novolac resin and other polyphenol compounds, and their modified products and other phenolic curing agents; BF3-amine complex, guanidine derivatives, etc. These curing agents can be used alone or in combination of two or more.

[0146] When permeability is important, it is preferred that the curing agent other than the curing agent (β) further contains an acid anhydride curing agent (γ).

[0147] 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 further 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) to the aforementioned range, there is a tendency to fully promote the curing reaction and obtain better cured properties.

[0148] In the epoxy resin composition of the present embodiment, when other curing agents other than the curing agent (β) are 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 further 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 to the above range, there is a tendency to function as a curing catalyst for other curing agents, fully promote the curing reaction, and obtain better cured properties.

[0149] In the epoxy resin composition in which the curing agent (β) containing the amine imide compound of the present embodiment is used as a curing accelerator and the above-mentioned anhydride curing agent (γ) is used as a curing agent, the equivalent ratio (anhydride group / epoxy group) of the 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 further preferably 0.90 to 1.10.

[0150] When the usage-amounts of the epoxy resin (α) and the acid anhydride type curing agent (γ) are set in the said range, there exists a tendency for the curing reaction to be sufficiently accelerated|stimulated and better hardened|cured physical property to be obtained.

[0151] The epoxy resin composition of the present embodiment may further contain an inorganic filler as necessary. The inorganic filler is not particularly limited, and examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, and aluminum nitride.

[0152] In the epoxy resin composition of the present embodiment, the content of the inorganic filler is not particularly limited as long as it is a 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 usually preferably less than 90 mass %. 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 handling property is excellent.

[0153] The epoxy resin composition of the present embodiment may further contain other compounding agents such as flame retardant, silane coupling agent, release agent, pigment as needed. As long as they are in the range that can obtain the effect of the present embodiment, suitable substances can be appropriately selected. As flame retardant, there is no particular limitation, and examples thereof include halides, compounds containing phosphorus atoms, compounds containing nitrogen atoms, inorganic flame retardant compounds, etc.

[0154] 〔Cured product〕

[0155] 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 known method. For example, first, the epoxy resin, curing agent, and a curing accelerator, an inorganic filler and / or a compounding agent as required are fully mixed to obtain an epoxy resin composition using an extruder, a kneader, a roller, etc. Thereafter, the epoxy resin composition is molded using an injection mold or a transfer molding machine, a compression molding machine, an injection molding machine, etc., and further heated under the conditions of about 80 to 200° C. and about 2 to 10 hours, so that a cured product can be obtained.

[0156] In addition, a cured product can be obtained by, 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, methyl isobutyl ketone, etc. to obtain a solution. The obtained solution is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heated and dried to obtain a prepreg. Then, the obtained prepreg is subjected to hot press molding to obtain a cured product.

[0157] 〔use〕

[0158] The epoxy resin composition of the present 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, sealing materials for semiconductors, adhesives, printed substrates, coating materials, composite materials, and the like.

[0159] Among these, semiconductor sealing materials suitable for bottom filling, molding, etc.; conductive adhesives such as anisotropic conductive films (ACF); printed wiring boards such as solder resists and cover films; composite materials such as prepregs formed by impregnating epoxy resin compositions into glass fibers or carbon fibers.

[0160] (Adhesive)

[0161] The adhesive of the present embodiment preferably includes the epoxy resin composition of the present embodiment, and the curing agent (β) includes an amine imide compound represented by the formula (3). This can achieve an effect of improving permeability.

[0162] (Electronic components)

[0163] The cured product of the epoxy resin composition of this embodiment can be used for various electronic components. Examples thereof include, but are not limited to, semiconductor sealing materials such as bottom filling and molding; conductive adhesives such as ACF; printed wiring boards such as solder resists and cover films; composite materials such as prepregs impregnated with glass fibers, carbon fibers, etc.

[0164] Example

[0165] 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.

[0166] In addition, unless otherwise specified, the "parts" and "%" below are based on mass.

[0167] In the synthesis examples described below, amine imide compounds and amine imide compositions were synthesized. As physical properties of the amine imide compounds and amine imide compositions, viscosity at 25° C., melting point, and infrared absorption spectrum were measured.

[0168] [Method for measuring viscosity at 25°C]

[0169] 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 using an E-type viscometer (“TVE-35H” manufactured by Toki Sangyo Co., Ltd.) 15 minutes after the sample temperature reached 25° C.

[0170] In addition, in Table 1, "properties" show the state at 25°C.

[0171] [Method for determining melting point]

[0172] 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.

[0173] · Apparatus: Differential thermal and thermogravimetric simultaneous measurement apparatus ("TG / DTA7220" manufactured by Hitachi High-Technologies Corporation)

[0174] Sample mass: about 10 mg

[0175] Sample container: open aluminum pot

[0176] ·Measurement temperature: 40℃~240℃

[0177] Heating rate: 5℃ / min

[0178] Atmosphere gas: Nitrogen

[0179] Gas flow rate: 40mL / min

[0180] [Method for determining the decomposition temperature of the N-N bond]

[0181] The N-N bond decomposition peak temperature of the amine imide compound and the amine imide composition is set to the peak temperature (T peak The N-N bond decomposition start temperature is set as the exothermic peak start temperature (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 ).

[0182] <Measurement Conditions>

[0183] · Apparatus: Differential thermal and thermogravimetric simultaneous measurement apparatus ("TG / DTA7220" manufactured by Hitachi High-Technologies Corporation)

[0184] Sample mass: about 10 mg

[0185] Sample container: open aluminum pot

[0186] ·Measurement temperature: 40℃~240℃

[0187] Heating rate: 5℃ / min

[0188] Atmosphere gas: Nitrogen

[0189] Gas flow rate: 40mL / min

[0190] [Measurement method of infrared absorption spectrum]

[0191] The infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer ("FT / IR-410" manufactured by JASCO Corporation). The measurement sample was prepared by a liquid film method when the sample was liquid, and by a tablet method when the sample was solid.

[0192] The liquid film method is a method of using a rock salt plate that transmits infrared rays to hold the sample and prepare a film-shaped measurement sample.

[0193] 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.

[0194] Check if there is any -1 ~1620cm -1 The specific infrared absorption spectrum derived from the amine imide group was observed at .

[0195] [Measurement method of mass spectrometry]

[0196] The mass spectrometry was performed using a QDa detector manufactured by Waters as a mass spectrometry (MS) detector.

[0197] Acetonitrile was used as a measurement sample and the concentration was adjusted to about 0.25 mass %.

[0198] The liquid feeding conditions were changed from 90:10 = methanol: water at the beginning to 50:50 = methanol: water after 3 minutes. A peak was observed at about 0.1 to 0.5 minutes, and therefore, the peak was analyzed.

[0199] The mass spectrometry analysis conditions of the QDa detector of Waters Company were set as follows: Mass (m / z) ES+ 50-1250, capillary voltage 0.8 V, Cone voltage 25 V, and probe temperature 600°C.

[0200] Each compound uses the addition of H + The m / z of 1 was observed.

[0201] A 5 mM ammonium acetate / methanol solution was delivered at 0.45 mL / min to facilitate ionization.

[0202] In the following, amine imide compounds and amine imide compositions are prepared.

[0203] 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.

[0204] [Synthesis example 1]

[0205] 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-butyl alcohol 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-butyl alcohol, 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). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1573 cm -1 The measured value of . In mass spectrometry, 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.

[0206]

[0207] [Synthesis example 2]

[0208] 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-butyl alcohol 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-butyl alcohol, 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). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1576 cm -1The measured value of . In mass spectrometry, 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.

[0209]

[0210] [Synthesis example 3]

[0211] 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-butyl alcohol are mixed to obtain a solution. The solution is reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid is concentrated under reduced pressure at 55°C to distill off tert-butyl alcohol, by-product alcohol, and unreacted raw materials to obtain a liquid product. The product is 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 is 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). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1595 cm -1 The measured value of . In mass spectrometry, 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.

[0212]

[0213] [Synthesis Example 4]

[0214] 24.27 g (0.12 mol) of diethyl 1,3-acetonedicarboxylate, 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 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, 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.

[0215]

[0216] [Synthesis example 5]

[0217] 12.13 g (0.06 mol) of diethyl 1,3-acetonedicarboxylate, 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-butyl alcohol 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-butyl alcohol, 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 33.40 g (yield: 81.5%) of dark brown liquid amine imide compound E (compound E). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1586 cm -1 The measured value of . In mass spectrometry, 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.

[0218]

[0219] [Synthesis example 6]

[0220] 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-butyl alcohol are mixed to obtain a solution. The solution is reacted while being stirred at 55°C for 3 days to obtain a reaction liquid. The obtained reaction liquid is concentrated under reduced pressure at 55°C to distill off tert-butyl alcohol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. The product is 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 is 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, 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.

[0221]

[0222] [Synthesis Example 7]

[0223] 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 are mixed to obtain a solution. The solution is reacted while being stirred at 55°C for 4 days to obtain a reaction liquid. The obtained reaction liquid is 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 is 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 is 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). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1617 cm -1 The measured value of . In mass spectrometry, 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.

[0224]

[0225] [Synthesis example 8]

[0226] 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-butyl alcohol 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-butyl alcohol, 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 a brown liquid amine imide compound H (compound H). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1588 cm -1 The measured value of . In mass spectrometry, 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.

[0227]

[0228] [Synthesis Example 9]

[0229] 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 aforementioned infrared absorption spectrum measurement method, IR (neat): 1595 cm -1 The measured value of . In mass spectrometry, 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.

[0230]

[0231] [Synthesis Example 10]

[0232] 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 unreacted raw material residues to obtain an organic layer. The organic layer was concentrated under reduced pressure again 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, 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.

[0233]

[0234] [Synthesis Example 11]

[0235] 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 aforementioned infrared absorption spectrum measurement method, IR (neat): 1592 cm -1 The measured value of . In mass spectrometry, 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.

[0236]

[0237] [Synthesis Example 12]

[0238] 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 being stirred 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 concentrated under reduced pressure again at 55°C to obtain 12.22 g (yield: 85.7%) of a light yellow liquid amine imide compound O (compound O). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1592 cm -1 The measured value of . In mass spectrometry, a peak of m / z = 574.8 was observed. It was found that the amine imide compound О represented by the following formula was obtained.

[0239]

[0240] [Synthesis Example 13]

[0241] 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 being stirred at 55°C for 2 days to obtain a reaction liquid. 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 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 aforementioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1593 cm -1 The measured value of m / z=575.6 and 421.4 were observed in the mass spectrometry analysis. m / z=575.6 is the same structure as the amine imide compound O, and m / z=421.4 is a compound having a diol terminal structure on one side. It is known that the amine imide composition О2 represented by the following formula is obtained.

[0242]

[0243] [Synthesis Example 14]

[0244] 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 being stirred at 55°C for 2 days to obtain a reaction liquid. 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 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 aforementioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1592 cm -1 The measured value of m / z=575.6 and 421.4 were observed in the mass spectrometry. m / z=575.6 is the same structure as the amine imide compound O, and m / z=421.4 is a compound having a diol terminal structure on one side. It is known that the amine imide composition О3 represented by the following formula is obtained.

[0245]

[0246] [Synthesis Example 15]

[0247] 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 aforementioned infrared absorption spectrum measurement method, IR (neat): 1603 cm -1 The measured value of . In mass spectrometry, 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.

[0248]

[0249] [Synthesis Example 16]

[0250] 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 being stirred 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 aforementioned infrared absorption spectrum measurement method, IR (neat): 1603 cm -1 The measured value of . In mass spectrometry, 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.

[0251]

[0252] [Synthesis Example 17]

[0253] 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 unreacted raw material residues 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., 4.91 g of a light yellow liquid amine imide composition Q2 (compound Q2). Using the aforementioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1600 cm -1 The measured value of m / z=699.7 and 483.4 were observed in mass spectrometry. m / z=699.7 is the same structure as the amine imide compound Q, and m / z=483.4 is a compound having a diol terminal structure on one side. It is known that the amine imide composition Q2 represented by the following formula is obtained.

[0254]

[0255] [Synthesis Example 18]

[0256] 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 are mixed to obtain a solution. The solution is reacted while being stirred at 55°C for 1 day to obtain a reaction liquid. The obtained reaction liquid is 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 is repeatedly washed with hexane to remove unreacted raw material residues to obtain an organic layer. The organic layer is concentrated under reduced pressure again at 55°C to obtain 4.87 g (yield: 60.7%) of a light yellow liquid amine imide compound R (compound R). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1578 cm -1 The measured value of . In mass spectrometry, 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.

[0257]

[0258] [Synthesis Example 19]

[0259] 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 being stirred at 55°C for 1 day to obtain a 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 10.06 g (yield: 81.3%) of a light yellow liquid amine imide compound S (compound S). Using the aforementioned infrared absorption spectrum measurement method, IR (neat): 1578 cm -1 The measured value of . In mass spectrometry, a peak of m / z=659.7 was observed. It was found that the amine imide compound S represented by the following formula was obtained.

[0260]

[0261] [Synthesis Example 20]

[0262] 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 being stirred at 55°C for 1 day to obtain a 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 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). Using the aforementioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1578 cm -1 The measured value of m / z=659.6 and 477.5 were observed in mass spectrometry. 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. It is known that the amine imide composition S2 represented by the following formula is obtained.

[0263]

[0264] [Synthesis Example 21]

[0265] 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 being stirred at 55°C for 1 day to obtain a 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 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 aforementioned infrared absorption spectrum measurement method, IR (neat) was obtained: 1578 cm -1 The measured value of m / z=659.6 and 477.5 were observed in the mass spectrometry. 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. It is known that the amine imide composition S3 represented by the following formula is obtained.

[0266]

[0267] [Synthesis Example 22]

[0268] 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-butyl alcohol are mixed to obtain a solution. The solution is reacted while being stirred at 55°C for 3 days to obtain a reaction liquid. The obtained reaction liquid is concentrated under reduced pressure at 55°C to distill off tert-butyl alcohol, by-product alcohol, and unreacted raw materials, thereby obtaining a solid product. The product is 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 is 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, 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.

[0269]

[0270] [Synthesis Example 23]

[0271] 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-butyl alcohol 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-butyl alcohol, by-product alcohol, and unreacted raw materials, thereby obtaining a solid product. The product was recrystallized using ethyl acetate to obtain 30.11 g (yield: 72.0%) of a white crystalline solid amine imide compound J (Compound J). Using the aforementioned infrared absorption spectrum measurement method, IR (KBr): 1594 cm -1 The measured value of . In mass spectrometry, 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.

[0272]

[0273] [Synthesis Example 24]

[0274] 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-butyl alcohol 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-butyl alcohol, 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, 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.

[0275]

[0276] [Comparative Synthesis Example 1]

[0277] 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 being stirred 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 to obtain 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. In mass spectrometry, a peak of m / z=294.4 was observed.

[0278]

[0279] The evaluation results of Synthesis Examples 1 to 24 and Comparative Synthesis Example 1 are shown in Table 1 below.

[0280] [Table 1]

[0281]

[0282] 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.

[0283] The epoxy resin composition was measured for various properties, namely, curability and storage stability at room temperature (25° C.).

[0284] [Preparation of epoxy resin composition (1)]

[0285] The epoxy resin compositions prepared in the following examples and comparative examples used the following epoxy resins as raw materials.

[0286] Epoxy resin: "BE-186EL" from Chang Chun Plastics Co., Ltd

[0287] When various raw materials are mixed, the amine imide compound, amine imide composition or acrylate-imidazole adduct is added in an amount of 2 to 20 parts by mass relative to 100 parts by mass of the epoxy resin. An epoxy resin and an amine imide compound, amine imide composition or acrylate-imidazole adduct are added to a plastic stirring container, and the mixture is stirred and mixed using a rotation / revolution stirrer ("ARE-310" manufactured by THINKY Corporation) to prepare an epoxy resin composition.

[0288] [Evaluation method of curability (1)]

[0289] 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.

[0290] The reaction rate was judged as “◎” when it was 95% or more, “○” when it was less than 95% and 90% or more, “△” when it was less than 90% and 80% or more, and “×” when it was less than 80%.

[0291] [Evaluation method for storage stability (1)]

[0292] As a method for evaluating storage stability (1), the viscosity of the epoxy resin composition at 25°C just 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.

[0293] 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.

[0294] [Example 1]

[0295] 20 g of epoxy resin ("BE-186EL" manufactured by Chang Chun Plastics Co., Ltd.) and 1.6 g of 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 by the above-mentioned curability evaluation method (1), and the storage stability at room temperature was evaluated by the above-mentioned storage stability evaluation method (1).

[0296] [Example 2]

[0297] 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.

[0298] [Example 3]

[0299] 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.

[0300] [Example 4]

[0301] 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.

[0302] [Example 5]

[0303] 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.

[0304] [Example 6]

[0305] Except having changed the amine imide compound A into the amine imide compound C, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0306] [Example 7]

[0307] Except having changed the amine imide compound A into the amine imide compound D, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0308] [Example 8]

[0309] Except having changed the amine imide compound A into the amine imide compound E, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0310] [Example 9]

[0311] 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.

[0312] [Example 10]

[0313] 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.

[0314] [Example 11]

[0315] 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.

[0316] [Example 12]

[0317] Except having changed the amine imide compound A into the amine imide compound H, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0318] [Example 13]

[0319] Except having changed the amine imide compound A into the amine imide compound L, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0320] [Example 14]

[0321] Except having changed the amine imide compound A into the amine imide compound M, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0322] [Example 15]

[0323] 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.

[0324] [Example 16]

[0325] 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.

[0326] [Example 17]

[0327] Except having changed the amine imide compound A into the amine imide compound O, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0328] [Example 18]

[0329] Except having changed the amine imide compound A into the amine imide compound O, it carried out similarly to Example 2, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0330] [Example 19]

[0331] Except having changed the amine imide compound A into the amine imide composition O2, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0332] [Example 20]

[0333] Except having changed the amine imide compound A into the amine imide composition O3, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0334] [Example 21]

[0335] Except having changed the amine imide compound A into the amine imide composition O3, it carried out similarly to Example 2, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0336] [Example 22]

[0337] Except having changed the amine imide compound A into the amine imide compound P, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0338] [Example 23]

[0339] 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.

[0340] [Example 24]

[0341] Except having changed the amine imide compound A into the amine imide composition Q2, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0342] [Example 25]

[0343] Except having changed the amine imide compound A into the amine imide compound R, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0344] [Example 26]

[0345] Except having changed the amine imide compound A into the amine imide compound R, it carried out similarly to Example 2, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0346] [Example 27]

[0347] Except having changed the amine imide compound A into the amine imide compound S, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0348] [Example 28]

[0349] Except having changed the amine imide compound A into the amine imide compound S, it carried out similarly to Example 2, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0350] [Example 29]

[0351] Except having changed the amine imide compound A into the amine imide composition S2, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0352] [Example 30]

[0353] Except having changed the amine imide compound A into the amine imide composition S2, it carried out similarly to Example 2, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0354] [Example 31]

[0355] Except having changed the amine imide compound A into the amine imide composition S3, it carried out similarly to Example 2, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0356] [Example 59]

[0357] 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 the storage stability at room temperature were evaluated.

[0358] [Example 60]

[0359] Except having changed the amine imide compound A into the amine imide compound J, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0360] [Example 61]

[0361] Except having changed the amine imide compound A into the amine imide compound K, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0362] [Comparative Example 1]

[0363] Except that the amine imide compound A was changed to DBU ("diazabicycloundecene" manufactured by Tokyo Chemical Industry Co., Ltd.), an epoxy resin composition was prepared in the same manner as in Example 1, and the curability and storage stability at room temperature were evaluated.

[0364] [Comparative Example 2]

[0365] Except having changed the amine imide compound A into DBU-phenolate ("U-CAT SA1" manufactured by SUN-PRO), it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and storage stability at room temperature.

[0366] [Comparative Example 3]

[0367] Except having changed the amine imide compound A into the acrylate-imidazole adduct, it carried out similarly to Example 1, and prepared the epoxy resin composition, and evaluated the curability and the storage stability at room temperature.

[0368] The evaluation results of Examples 1 to 31, 59 to 61, and Comparative Examples 1 to 3 are shown in Tables 2 to 6.

[0369] [Table 2]

[0370]

[0371] [Table 3]

[0372]

[0373] [Table 4]

[0374]

[0375] [Table 5]

[0376]

[0377] [Table 6]

[0378]

[0379] [Preparation of epoxy resin composition (2)]

[0380] The epoxy resin compositions prepared in the following examples and comparative examples used the following epoxy resins and acid anhydrides as raw materials.

[0381] Epoxy resin: "BE-186EL" from Chang Chun Plastics Co., Ltd

[0382] Acid anhydride: "HN-5500" manufactured by Hitachi Chemical Co., Ltd.

[0383] 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.

[0384] In addition, each raw material was added in the compounding amount shown in Table 7 to Table 9 with respect to 100 parts by mass of the epoxy resin.

[0385] 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, and the mixture is stirred and mixed using a rotation / revolution stirrer ("ARE-310" manufactured by THINKY Co., Ltd.), thereby premixing the epoxy resin and the amine imide compound, etc. Next, a predetermined amount of anhydride is added to the premix, and the mixture is further stirred and mixed, thereby preparing an epoxy resin composition.

[0386] [Evaluation method of curability (2)]

[0387] As a method for evaluating curability (2), the prepared epoxy resin composition was heated and evaluated under the following conditions. With respect to the temperature at which 100 Pa·s was reached, the case of less than +15°C was judged as "◎", the case of more than +15°C and less than +30°C was judged as "○", the case of more than +30°C and less than +45°C was judged as "△", and the case of more than +45°C was judged as "×".

[0388] <Measurement Conditions>

[0389] · Apparatus: Viscoelasticity measuring apparatus ("HAAKE MARS" manufactured by Thermo Scientific)

[0390] Sample mass: about 0.5mL

[0391] Plate shape: parallel

[0392] ·Measurement mode: constant shear rate (dγ / dt=1.0s -1 )

[0393] ·Measurement temperature: 40℃~240℃

[0394] Heating rate: 5℃ / min

[0395] [Evaluation method for storage stability (2)]

[0396] As a storage stability evaluation method (2), 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 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. The case where the viscosity increase ratio is less than 3.0 times is judged as "◎", the case where it is 3.0 times or more and less than 7.0 times is judged as "○", the case where it is 7.0 times or more and less than 10.0 times is judged as "△", and the case where it is 10.0 times or more is judged as "×".

[0397] [Evaluation method for prepreg surface smoothness]

[0398] The prepared epoxy resin composition was applied to a carbon fiber cloth ("TORAYCA CLOTH CO6343" manufactured by Toray Industries, Inc.) (weight per unit area: 198 g / m 2 ) for 5 minutes, and heated in an oven at 170°C for 10 minutes to prepare a prepreg. In addition, the surface state of the obtained prepreg was observed. The surface was judged as "○" when it was smooth, and the surface was judged as "×" when unevenness due to pores was observed.

[0399] [Evaluation method of prepreg adhesion]

[0400] The prepared epoxy resin composition was applied to a carbon fiber cloth ("TORAYCA CLOTH CO6343" manufactured by Toray Industries, Inc.) (weight per unit area: 198 g / m 2 ) for 5 minutes, and heated in an oven at 170°C for 10 minutes to prepare a prepreg. The stickiness of the obtained prepreg was confirmed. The case of no stickiness was judged as "○", and the case of stickiness was judged as "×".

[0401] [Evaluation method of permeability]

[0402] A carbon fiber cloth ("TORAYCA CLOTHCO6343" manufactured by Toray Industries, Inc.) (weight per unit area: 198 g / m2) was sandwiched between the pressure filters as filter cloth. 2 ), the prepared epoxy resin composition was pressure filtered using 0.2L / min nitrogen at room temperature. 10 mg of the epoxy resin composition obtained in the form of filtrate was weighed into an aluminum container of a differential scanning calorimeter ("DSC220C" manufactured by SII), heated in an oven at 180°C for 1.5 hours, and then quenched. The reaction rate was calculated based on the change in DSC heat before and after filtration. The case where the reaction rate was 95% or more was judged as "○", and the case where it was less than 95% was judged as "×".

[0403] It should be noted that in this evaluation, when an amine imide compound or the like is used as a curing accelerator, when the permeability of the curing accelerator is excellent, there is no difference in the amount of the curing accelerator in the epoxy resin composition before and after the pressure filtration, and it can be confirmed that the desired reactivity can be obtained. On the other hand, when the permeability of the curing accelerator is poor, at least a part of the curing accelerator is captured by the carbon fiber cloth, and the curing accelerator in the epoxy resin composition after the pressure filtration is reduced, and it can be confirmed that the desired reactivity cannot be obtained.

[0404] [Example 32]

[0405] 20 g of epoxy resin ("BE-186EL" manufactured by Chang Chun Plastics Co., Ltd.) and 0.6 g of 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). Next, 17.9 g of 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 by the above-mentioned curability evaluation method (2), and the storage stability at room temperature was evaluated by the above-mentioned storage stability evaluation method (2). In addition, the prepreg surface smoothness, prepreg viscosity, and permeability were also evaluated.

[0406] [Example 33]

[0407] 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.

[0408] [Example 34]

[0409] 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 adhesion, and permeability were evaluated.

[0410] [Example 35]

[0411] The 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 amount of the amine imide compound B added was changed to 3.6 g, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0412] [Example 36]

[0413] The 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 amount of the amine imide compound B added was changed to 4.8 g, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0414] [Example 37]

[0415] The 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 amount of the amine imide compound C added was changed to 0.2 g, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0416] [Example 38]

[0417] 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 adhesion, and permeability were evaluated.

[0418] [Example 39]

[0419] 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 adhesion, and permeability were evaluated.

[0420] [Example 40]

[0421] 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 adhesion, and permeability were evaluated.

[0422] [Example 41]

[0423] 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 adhesion, and permeability were evaluated.

[0424] [Example 42]

[0425] The 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 addition amount of the amine imide compound F was changed to 2.0 g, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0426] [Example 43]

[0427] 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 adhesion, and permeability were evaluated.

[0428] [Example 44]

[0429] The 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 amount of the amine imide compound H added was changed to 0.2 g, and the curing property, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0430] [Example 45]

[0431] Except that the amine imide compound A was changed to the amine imide compound H, an epoxy resin composition was prepared in the same manner as in Example 32, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0432] [Example 46]

[0433] Except that the amine imide compound A was changed to the amine imide compound L, an epoxy resin composition was prepared in the same manner as in Example 32, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0434] [Example 47]

[0435] 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 adhesion, and permeability were evaluated.

[0436] [Example 48]

[0437] Except that the amine imide compound A was changed to the amine imide compound N, an epoxy resin composition was prepared in the same manner as in Example 32, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0438] [Example 49]

[0439] 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 adhesion, and permeability were evaluated.

[0440] [Example 50]

[0441] 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 adhesion, and permeability were evaluated.

[0442] [Example 51]

[0443] 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 adhesion, and permeability were evaluated.

[0444] [Example 52]

[0445] Except that the amine imide compound A was changed to the amine imide compound P, an epoxy resin composition was prepared in the same manner as in Example 32, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0446] [Example 53]

[0447] 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 adhesion, and permeability were evaluated.

[0448] [Example 54]

[0449] 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 adhesion, and permeability were evaluated.

[0450] [Example 55]

[0451] Except that the amine imide compound A was changed to the amine imide compound R, an epoxy resin composition was prepared in the same manner as in Example 32, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0452] [Example 56]

[0453] 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 adhesion, and permeability were evaluated.

[0454] [Example 57]

[0455] 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 adhesion, and permeability were evaluated.

[0456] [Example 58]

[0457] 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 adhesion, and permeability were evaluated.

[0458] [Example 62]

[0459] 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 adhesion, and permeability were evaluated.

[0460] [Example 63]

[0461] 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 adhesion, and permeability were evaluated.

[0462] [Example 64]

[0463] 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 adhesion, and permeability were evaluated.

[0464] [Comparative Example 4]

[0465] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to DBU ("diazabicycloundecene" manufactured by Tokyo Chemical Industry Co., Ltd.), and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0466] [Comparative Example 5]

[0467] An epoxy resin composition was prepared in the same manner as in Example 32 except that the amine imide compound A was changed to DBU-phenolate ("U-CAT SA1" manufactured by SUN-PRO), and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0468] [Comparative Example 6]

[0469] Except that the amine imide compound A was changed to the acrylate-imidazole adduct A, an epoxy resin composition was prepared in the same manner as in Example 32, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg adhesion, and permeability were evaluated.

[0470] [Comparative Example 7]

[0471] 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 curability, storage stability at room temperature, prepreg surface smoothness, prepreg viscosity, and permeability were evaluated.

[0472] The evaluation results of Examples 32 to 58, 62 to 64, and Comparative Examples 4 to 7 are shown in Tables 7 to 9.

[0473] [Table 7]

[0474]

[0475] [Table 8]

[0476]

[0477] [Table 9]

[0478]

[0479] From the results of Tables 1 to 9, it was confirmed that the epoxy resin compositions of Examples 1 to 64 obtained using the amine imide compounds obtained in Synthesis Examples 1 to 24 or the amine imide compositions A to S3 were excellent in curability and storage stability.

[0480] Furthermore, from the results of Tables 7 to 9, it was confirmed 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 had excellent permeability and exhibited good prepreg characteristics.

[0481] On the other hand, it was confirmed that the epoxy resin compositions of Comparative Examples 1 to 7 were excellent in curability, but were inferior in storage stability at room temperature.

[0482] [Measurement method of shear bond strength]

[0483] The tensile shear bond strength with respect to the steel plate was measured in accordance with JIS K6850.

[0484] The shear adhesion evaluation was performed using the epoxy resin compositions of Examples 65 to 68 prepared as follows.

[0485] [Examples 65 to 76]

[0486] 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.

[0487] The prescribed amine imide compound shown in the following Table 10 was added in an amount of 20 parts by mass relative to 100 parts by mass of the total epoxy resin. Acrylate-imidazole was added in an amount of 10 parts by mass. The epoxy resin and the amine imide compound were placed in a plastic stirring container and stirred and mixed with a rotation / revolution stirrer ("ARE-310" manufactured by THINKY Corporation) to prepare an epoxy resin composition.

[0488] The epoxy resin composition prepared as above was applied between two steel plate test pieces (SPCC-SB: manufactured by Standard-Testpiece Co., Ltd.) with a bonding area of ​​12.5 mm × 5 mm, and then heated at a set temperature of 150° C. for 2 hours in a heating furnace to perform thermal curing and bonding to obtain a test piece. The tensile shear bonding strength of the obtained test piece was measured in a constant temperature and humidity room at 23° C. and 50% RH using AUTOGRAPH AGS-X 5kN (manufactured by Shimadzu Corporation), and the median value of the obtained values ​​was taken as the tensile shear bonding strength to the steel plate substrate.

[0489] [Table 10]

[0490]

[0491] 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 - -N + The shear bonding strength of the structure (amine imide compounds О, M, etc.) under the same curing conditions becomes higher. The reason for this is believed to be that there are multiple -N - -N + -, the active ingredients in the curing agent mass increase.

[0492] This application is based on Japanese Patent Application (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.

[0493] Industrial Applicability

[0494] 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 resists and cover films, composite materials such as prepregs impregnated with glass fibers or carbon fibers, etc.

Claims

1. An amine imide compound represented by the following formula (3): In formula (3), R1 each independently represents a hydrogen atom, or a monovalent hydrocarbon group having 1 to 15 carbon atoms and optionally having a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R2 and R3 each independently represent an alkyl group, an aryl group, an aralkyl group having 1 to 12 carbon atoms, which is unsubstituted or has a substituent, or a heterocycle having 7 or less carbon atoms formed by connecting R2 and R3, wherein the substituent each independently represents a halogen atom, an alkoxy group, a carbonyl group, a cyano group, an azo group, an azido group, a thiol group, a sulfone group, a nitro group, a hydroxyl group, an acyl group or an aldehyde group; R4 is an n-valent organic group having 1 to 30 carbon atoms and optionally containing an oxygen atom; and n is 2 or 3.

2. The amine imide compound according to claim 1, wherein The R1 in the formula (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.

3. The amine imide compound according to claim 2, wherein In formula (5), n is 0 or 1.

4. The amine imide compound according to any one of claims 1 to 3, wherein At least one of R2 and R3 represents an aralkyl group.

5. 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 (3) + The heterocyclic ring formed In formula (8), R 23 Indicates that N + A group that together forms a heterocyclic structure.

6. 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 (3) + The heterocyclic ring formed In formula (8), R 23 Indicates that N + A group that together forms a heterocyclic structure.

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

8. The amine imide compound according to any one of claims 1 to 3, wherein In the formula (3), n is 2. 9 . The amine imide compound according to claim 1 , which has a viscosity at 25° C. of 1300 Pa·s or less. 10 . The amine imide compound according to claim 9 , which has a viscosity at 25° C. of 900 Pa·s or less. 11 . The amine imide compound according to claim 9 , which has a viscosity at 25° C. of 800 Pa·s or less. 12 . The amine imide compound according to claim 9 , which has a viscosity at 25° C. of 700 Pa·s or less.

13. 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.

14. The amine imide compound according to claim 13, 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 It is 5°C or higher and 40°C or lower.

15. The amine imide compound according to claim 13, 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 It is 10°C or higher and 35°C or lower.

16. The amine imide compound according to claim 13, 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 It is 15°C or higher and 30°C or lower.

17. The amine imide compound according to claim 13, wherein The T peak is 100°C or more and 250°C or less, the T onset It is 80°C or higher and 200°C or lower.

18. The amine imide compound according to claim 13, wherein The T peak is 100°C or more and 220°C or less, the T onset It is 80°C or higher and 185°C or lower.

19. The amine imide compound according to claim 13, wherein The T peak is 100°C or more and 200°C or less, the T onset It is 80°C or higher and 170°C or lower.

20. The amine imide compound according to claim 13, wherein The T peak is 100°C or more and 180°C or less, the T onset It is 80°C or higher and 160°C or lower.

21. An amine imide composition comprising a plurality of amine imide compounds selected from the group consisting of the amine imide compound according to any one of claims 1 to 20 and amine imide compounds represented by the following formula (1) and formula (2), In formula (1) and (2), R1 each independently represents a hydrogen atom, or a monovalent organic group or n-valent organic group having 1 to 15 carbon atoms and optionally having a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R2 and R3 each independently represent an alkyl group, an aryl group, an aralkyl group having 1 to 12 carbon atoms, which is unsubstituted or substituted, or a heterocycle having 7 or less carbon atoms formed by connecting R2 and R3, wherein the substituents each independently represent a halogen atom, an alkoxy group, a carbonyl group, a cyano group, an azo group, an azido group, a thiol group, a sulfone group, a nitro group, a hydroxyl group, an acyl group or an aldehyde group; R4 each independently represents a hydrogen atom, or a monovalent organic group having 1 to 30 carbon atoms and optionally containing an oxygen atom; n is 2 or 3, At least one of the plurality of amine imide compounds is the amine imide compound represented by formula (3). 22 . The amine imide composition according to claim 21 , comprising the amine imide compounds represented by the formula (1) and the formula (3). 23 . A curing agent comprising the amine imide compound according to claim 1 , or the amine imide composition according to claim 21 or 22 . An epoxy resin composition comprising an epoxy resin α and the curing agent β according to claim 23.

25. The epoxy resin composition according to claim 24, 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.

26. The epoxy resin composition according to claim 25, 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.

27. The epoxy resin composition according to claim 25, 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. 28 . The epoxy resin composition according to claim 24 , further comprising an anhydride-based curing agent γ.

29. A method for producing an amine imide compound, which is a method for producing the amine imide compound according to any one of claims 1 to 20, or the amine imide compound in the amine imide composition according to claim 21 or 22, The method comprises a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B) and a glycidyl ether compound (C). 30 . A sealing material which is a cured product of the epoxy resin composition according to claim 24 .

31. An adhesive comprising the epoxy resin composition according to claim 24.

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