Aminimide compound, aminimide composition, curing agent, epoxy resin composition, method for producing aminimide compound, sealing material, and adhesive

Abstract

To provide an aminimide compound which is excellent in penetrability, and has excellent curability and storage stability.SOLUTION: An aminimide compound is represented by the following formula (1), (2) or (3).SELECTED DRAWING: None

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 an amine imide compound, a sealing material, and an adhesive. [Background technology]

[0002] Epoxy resins have been used in a wide range of applications, such as coating materials, electrical and electronic insulating materials, and adhesives, because their cured products have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesive properties, and the like. Epoxy resin compositions currently in general use are so-called two-part epoxy resin compositions in which two parts, an epoxy resin and a curing agent, are mixed at the time of use.

[0003] Although two-component epoxy resin compositions can be cured at room temperature, they have the disadvantage that the epoxy resin and the curing agent must be stored separately and must be measured and mixed each time they are used, making storage and handling cumbersome. Furthermore, since the usable time is limited, it is not possible to mix a large amount in advance.

[0004] In order to solve the problems of the two-component epoxy resin compositions as described above, several one-component epoxy resin compositions have been proposed (for example, see Patent Documents 1 to 3). For example, there is an epoxy resin composition in which a latent curing agent is blended with an epoxy resin.

[0005] In addition, the demands for electronic devices today are diverse, including miniaturization, high functionality, weight reduction, high functionality, and multi-function, and for example, even in semiconductor chip mounting technology, there is a demand for finer electrode pads and pad pitches for finer fineness, miniaturization, and high density. Therefore, underfill, which is an adhesive used in the gap between the chip and the substrate, is required to penetrate into narrower gaps. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6282515 [Patent Document 2] JP 2003-96061 A [Patent Document 3] JP 2000-229927 A Summary of the Invention [Problem to be solved by the invention]

[0007] A latent curing agent constituting a one-component epoxy resin composition is required to have both good curing properties and storage stability after mixing with an epoxy resin, and also to have good permeability into narrow gaps in electronic components and between dense fibers such as carbon fibers and glass fibers. However, a latent curing agent that satisfies all of these characteristics has not yet been obtained.

[0008] For example, Patent Document 1 discloses a liquid bisimidazole compound in which imidazole is modified with an acrylate as a curing agent, but the storage stability is problematic and there is room for improvement. Furthermore, Patent Document 2 discloses an amine imide compound using 1-aminopyrrolidine, but this has the problem that it is a solid and therefore has poor permeability at room temperature. Furthermore, Patent Document 3 discloses a liquid amine imide, but the compound has the problem that it is difficult to handle because it uses 1,1-dimethylhydrazine as a raw material, which is a self-reactive substance and is designated as a toxic substance.

[0009] In view of the above-mentioned problems in the prior art, an object of the present invention is to provide an amine imide compound which has excellent permeability, curability and storage stability. [Means for solving the problem]

[0010] As a result of extensive investigations, the present inventors have discovered that amine imides having specific structures are excellent in permeability, curability and storage stability, leading to the completion of the present invention. That is, the present invention is as follows.

[0011] [1] An amine imide compound represented by the following formula (1), (2) or (3):

[0012] [ka]

[0013] [ka]

[0014] [ka]

[0015] (In the formulas (1) to (3), R1's each independently represent a hydrogen atom, or a monovalent or n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or a heterocycle having 7 or less carbon atoms to which R2 and R3 are linked; R4's each independently represent a hydrogen atom, or a monovalent or n-valent organic group having 1 to 30 carbon atoms which may have an oxygen atom, and n represents an integer of 1 to 3.)

[0016] [2] The amine imide compound according to [1] above, wherein R1 in formula (1) or (3) is a group represented by formula (4) or (5):

[0017] [ka]

[0018] [ka]

[0019] (In formulas (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 each n independently represents an integer of 0 to 6.

[0020] [3] The amine imide compound according to [1] above, wherein R1 in formula (2) is a group represented by formula (6) or (7):

[0021] [ka]

[0022] [ka]

[0023] (In formulas (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.

[0024] [4]

[0023] At least one of R2 and R3 represents an aralkyl group. [5] The heterocycle having 7 or less carbon atoms to which R2 and R3 are linked is represented by the following formula (8), 23 and N in formula (1), (2) or (3) +

[0021] (1) wherein R is an integer of 1 to 3; and R is an integer of 1 to 3.

[0025] [ka]

[0026] (In formula (8), R 23 is N + represents a group which, together with

[0027] [6] The amine imide compound according to any one of [1] to [5] above, wherein R4 in 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. [7] The amine imide compound according to any one of [1] to [5] above, wherein R4 in formula (3) is a group represented by formula (9) or (10):

[0028] [ka]

[0029] [ka]

[0030] (In formulas (9) and (10), R 41 and R 42 each independently represents an alkyl group, an aryl group, or an aralkyl group having 1 to 5 carbon atoms, and each n independently represents an integer of 0 to 10.

[0031] [8] The amine imide compound according to any one of [1] to [7] above, which is represented by formula (2) or (3) above, wherein n is 2 or 3. [9] The amine imide compound according to any one of [1] to [7] above, which is represented by formula (2) or (3) above, wherein n is 2.

[10] The amine imide compound according to any one of [1] to [9] above, which has a viscosity at 25° C. of 1,300 Pa·s or less.

[11] The top temperature of the exothermic peak associated with the decomposition of the NN bond in differential thermal analysis (T peak ) and rise temperature (T onset ) and the difference (T peak -T onset 11. The amine imide compound according to any one of [1] to

[10] above, wherein the temperature (T) of the reaction mixture is 45° C. or lower.

[12]

[0023] An amine imide composition comprising a plurality of amine imide compounds according to any one of [1] to

[11] above.

[13] The amine imide composition according to

[12] above, which contains amine imide compounds represented by formulas (1) and (3).

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

[10] above or the amine imide composition according to

[12] or

[13] above.

[15] An epoxy resin (α), The curing agent (β) according to

[14] above, , including, Epoxy resin composition.

[16] The epoxy resin composition according to

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

[17] The epoxy resin composition according to

[15] or

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

[18] A method for producing an amine imide as described in any one of [1] to

[11] above, or an amine imide in an amine imide composition as described in

[12] or

[13] above, comprising the steps of: The method includes a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B), and a glycidyl ether compound (C), Method for producing amine imides.

[19] An encapsulant comprising a cured product of the epoxy resin composition according to any one of

[15] to

[17] .

[20] An adhesive comprising the epoxy resin composition according to

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

[0032] According to the present invention, it is possible to provide a latent curing agent having excellent permeability, curing property and storage stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] Hereinafter, an embodiment for carrying out the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its purpose.

[0034] [Amine imide compounds] The amine imide of this embodiment is represented by formula (1), (2) or (3):

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] (In the formulas (1) to (3), R1's each independently represent a hydrogen atom, or a monovalent or n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or a heterocycle having 7 or less carbon atoms to which R2 and R3 are linked; R4's each independently represent a hydrogen atom, or a monovalent or n-valent organic group having 1 to 30 carbon atoms which may have an oxygen atom, and n represents an integer of 1 to 3.)

[0039] The amine imide of this embodiment does not have any substituents capable of curing when in the amine imide compound state, and therefore does not undergo an addition reaction with epoxy groups even when it is made compatible with epoxy resins at room temperature. However, as shown in the reaction formula below, heating cleaves the N-N bond to generate an acylnitrene and a tertiary amine. The acylnitrene further undergoes a 1,2-transfer reaction to become an isocyanate. The isocyanate and tertiary amine thus generated have curing properties and undergo an addition reaction with epoxy groups to result in curing. In other words, the amine imide of this embodiment functions as a latent curing agent.

[0040] [ka]

[0041] Furthermore, because the amine imide of this embodiment contains a hydroxyl group, upon heating, the generated isocyanate undergoes an addition reaction with a tertiary amine, resulting in a structure containing a tertiary amine and a urethane bond per molecule, as represented by the following reaction formula: This structure has better curing performance than isocyanate and tertiary amine, and the amine imide of this embodiment therefore functions as a latent curing agent with excellent curing performance.

[0042] [ka]

[0043] The compound represented by formula (2) is a compound in which the compound represented by formula (1) is linked by an n-valent linking group R1, and the compound represented by formula (3) is a compound in which the compound represented by formula (1) is linked by 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.

[0044] The peak temperature (T peak ) is preferably 100°C or higher and 250°C or lower, more preferably 100°C or higher and 220°C or lower, even more preferably 100°C or higher and 200°C or lower, and even more preferably 100°C or higher and 180°C or lower. T peak When the temperature is 100° C. or higher, the storage stability tends to be improved. peak By keeping the temperature at or below 250°C, the curing performance of the amine imide tends to be improved. peak ) is the top 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.

[0045] The decomposition temperature rise temperature (T onset ) is preferably 80°C or higher and 200°C or lower, more preferably 80°C or higher and 185°C or lower, even more preferably 80°C or higher and 170°C or lower, and even more preferably 80°C or higher and 160°C or lower. T onset When the temperature is 80° C. or higher, the storage stability tends to be improved. onset By keeping the temperature at or below 200°C, the curing performance of the amine imide tends to be improved. onset) refers to the rise temperature of an exothermic peak in differential thermal analysis. More specifically, the intersection point between the tangent of the maximum slope of the rise part of the exothermic peak and the extrapolated line of the baseline is called the rise temperature (T onset )

[0046] The peak temperature (T peak ) and the rise temperature (T onset ) difference (T peak -T onset ) is preferably 45° C. or less, more preferably 40° C. or less, even more preferably 35° C. or less, and even more preferably 30° C. or less. peak -T onset ) is 45°C or less, the decomposition of the NN bond by heating proceeds quickly, and the reaction steepness of the curing reaction tends to be improved. peak -T onset ) is not particularly limited, but is preferably 5° C. or higher, more preferably 10° C. or higher, and even more preferably 15° C. or higher.

[0047] Peak temperature (T peak ), rise temperature (T onset ), and the difference (T peak -T onset ) can be controlled by adjusting the functional groups of the amine imide of this embodiment. For example, R1 contributes to lowering the energy of the cleavage of the N-N bond, and R2 and R3 tend to contribute to lowering the energy of the cleavage reaction due to instability caused by steric hindrance. Thus, these temperatures can be controlled by using an appropriate combination of groups that contribute to improved curing performance and other groups as R1, R2 and R3, which will be described later.

[0048] The amine imide of this embodiment is preferably a liquid compound at room temperature. In this embodiment, the viscosity at 25° C. can be used as an index showing whether a compound is in a liquid state at room temperature. The viscosity of the amine imide of this embodiment at 25° C. is preferably 1300 Pa·s or less, more preferably 900 Pa·s or less, even more preferably 800 Pa·s or less, and even more preferably 700 Pa·s or less. Although there is no particular lower limit for the viscosity at 25° C., it is preferable that the viscosity is 0.01 Pa·s or more. The amine imide of this embodiment is a liquid compound at room temperature, and in particular has a viscosity of 1,300 Pa s or less at 25°C, which improves the solubility and dispersibility in epoxy resin compositions and the permeability into substrates and the like. The viscosity of the amine imide of this embodiment can be controlled within the above range by adjusting the functional groups R1 to R4 in formulas (1) to (3).

[0049] In formula (1), (2) or (3), R1 contributes to lowering the energy of cleavage of the N-N bond, R2 and R3 contribute to lowering the energy of the cleavage reaction by destabilization due to steric hindrance, and R4 contributes to liquefying the compound and suppressing the decrease in the glass transition temperature of the obtained cured product, but is not particularly limited. Details of each group will be described below.

[0050] In formulae (1), (2), and (3), R1 each independently represents a hydrogen atom, or a monovalent or n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond. Examples of such organic groups include, but are not limited to, 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 a hydrocarbon group is substituted with an ester bond or an ether bond. Examples of such hydrocarbon groups include linear, branched, or cyclic alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups; alkenyl groups, such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, decynyl, dodecynyl, hexadecynyl, and octadecynyl groups; aryl groups, such as phenyl; and aralkyl groups consisting of a combination of an alkyl group and a phenyl group, such as methylphenyl, ethylphenyl, and propylphenyl groups.

[0051] The organic group represented by R1 may have other substituents, which are not particularly limited and include, for example, halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azido groups, thiol groups, sulfo groups, nitro groups, hydroxy groups, acyl groups, and aldehyde groups.

[0052] The organic group represented by R1 has 1 to 15 carbon atoms, preferably 1 to 12, and more preferably 1 to 7. When the number of carbon atoms in the organic group represented by R1 is within this range, a liquid amine imide satisfying the above-mentioned viscosity is more easily obtained, and the curing performance of the amine imide tends to be improved. Furthermore, when the number of carbon atoms in the organic group represented by R1 is within this range, the availability of raw materials is improved.

[0053] Among the above, R1 in formula (1) or (3) is preferably a group represented by the following formula (4) or (5): The presence of such a group makes it easier to obtain a liquid amine imide satisfying the above viscosity requirement, and also tends to improve the curing performance of the amine imide.

[0054] [ka]

[0055] [ka]

[0056] (In formulas (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 each n independently represents an integer of 0 to 6.

[0057] Among the above, preferred are groups of formula (5) where n is 0 or 1. This gives the compound represented by formula (1) or (3) 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.

[0058] In addition, R in formula (4) or (5) 11 The number of carbon atoms and n are adjusted so that the maximum number of carbon atoms in the group represented by formula (4) or (5) does not exceed 15.

[0059] In addition, R1 in formula (2) is preferably a group represented by the following formula (6) or (7): The presence of such a group makes it easier to obtain a liquid amine imide satisfying the above-mentioned viscosity, and also tends to improve the curing performance of the amine imide.

[0060] [ka]

[0061] [ka]

[0062] (In formulas (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.

[0063] Among the above, in formula (7), R 13 is preferably a single bond or a methyl group. As a result, the compound represented by formula (2) 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.

[0064] In formulae (1), (2), and (3), R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or a heterocycle having 7 or less carbon atoms to which R2 and R3 are linked.

[0065] The alkyl group having 1 to 12 carbon atoms represented by R2 or R3 is not particularly limited, but examples thereof include linear alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched alkyl groups such as isopropyl, isobutyl, t-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. The alkyl group may be a combination of a linear or branched alkyl group and a cyclic alkyl group. The alkyl group may also contain an unsaturated bond group.

[0066] The number of carbon atoms in the alkyl groups represented by R2 or R3 is each independently 1 to 12, preferably 2 to 10, and more preferably 5 to 10. Asymmetric dialkylhydrazine compounds such as dimethylhydrazine in which the alkyl group has a small number of carbon atoms are explosive and toxic to the human body, but by ensuring that the alkyl group represented by R2 or R3 has 2 or more carbon atoms, it is possible to avoid the use of raw materials that pose such risks of toxicity, etc. Furthermore, by ensuring that the alkyl group represented by R2 or R3 has 5 or more carbon atoms, it is easier to obtain a liquid amine imide that satisfies the above-mentioned viscosity, and the curing performance of the amine imide tends to be further improved.

[0067] The aryl group represented by R2 or R3 is not particularly limited, but may be, for example, a phenyl group or a naphthyl group. The aralkyl group represented by R2 or R3 is not particularly limited, but may be, for example, a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, or a dimethylnaphthyl group. Of these, it is preferable that at least one of R2 and R3 is an aralkyl group, and a methylphenyl group (benzyl group) is more preferable. This tends to further improve the curing performance of the amine imide compound. The number of carbon atoms in the aryl group and aralkyl group represented by R2 or R3 is not particularly limited, but is preferably 6 to 20.

[0068] 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 sulfo group, a nitro group, a hydroxy group, an acyl group, and an aldehyde group.

[0069] R2 and R3 may be linked together to form a heterocycle having 7 or less carbon atoms. Such a heterocycle is not particularly limited, but examples thereof include R 23 and N in formula (1), (2) or (3) + In addition, examples of the heterocycle include a heterocycle formed by R 23 represents a group formed by linking R2 and R3.

[0070] [ka]

[0071] (In formula (8), R 23 is N + represents a group which, together with

[0072] R 23 and N + The heterocycle formed by these rings is not particularly limited, and examples thereof include 4-membered rings such as an azetidine ring; 5-membered rings such as a pyrrolidine ring, a pyrrole ring, a morpholine ring, and a thiazine ring; 6-membered rings such as a piperidine ring; and 7-membered rings such as a hexamethyleneimine ring and an azepine ring.

[0073] Among these, preferred heterocycles are pyrrole ring, morpholine ring, thiazine ring, piperidine ring, hexamethyleneimine ring and azepine ring, with 6-membered and 7-membered rings being more preferred. The presence of such groups makes it easier to obtain a liquid amine imide that satisfies the above-mentioned viscosity and also tends to improve the curing performance of the amine imide.

[0074] The substituent is not particularly limited, but may be, for example, an alkyl group, an aryl group, or the above-mentioned substituents in R2 and R3. Furthermore, when the heterocycle has an alkyl group as a substituent, N + and a methyl group bonded to the carbon atom adjacent to the carbon atom.

[0075] In formulae (1), (2), and (3), R4 represents a hydrogen atom or a monovalent or n-valent organic group having 1 to 30 carbon atoms which may contain an oxygen atom. Examples of such an organic group include, but are not limited to, 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, a carbonyl group, or a group containing a silicon atom, and a group in which a part of the carbon atoms constituting the hydrocarbon group is substituted with an ester bond, an ether bond, or a silicon atom. Examples of such hydrocarbon groups include linear, branched, or cyclic alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups; alkenyl groups, such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, decynyl, dodecynyl, hexadecynyl, and octadecynyl groups; aryl groups, such as phenyl groups; and aralkyl groups consisting of a combination of an alkyl group and a phenyl group, such as methylphenyl, ethylphenyl, and propylphenyl groups.

[0076] Furthermore, the hydrocarbon group represented by R4 includes bisphenol skeletons such as a bisphenol A skeleton, a bisphenol AP skeleton, a bisphenol B skeleton, a bisphenol C skeleton, a bisphenol E skeleton, and a bisphenol F skeleton. The organic group containing a 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.

[0077] Among these, the organic group represented by R4 in formula (1) or (2) is preferably an alkyl group, an alkenyl group, or an aralkyl group, more preferably an alkyl group or an alkenyl group, and even more preferably a branched alkyl group or a branched alkenyl group. These preferred groups may have a substituent. By having such a group, it becomes easier to obtain a liquid amine imide that satisfies the above viscosity, and the curing performance of the amine imide tends to be further improved. In addition, the Tg of the cured product obtained by using the amine imide tends to be further improved.

[0078] As mentioned above, the number of carbon atoms in the organic group represented by R4 is 1 to 30, preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. When the number of carbon atoms in the organic group represented by R4 is within this range, a liquid amine imide satisfying the above-mentioned viscosity is more easily obtained, and the curing performance of the amine imide tends to be further improved. In addition, the Tg of cured products obtained using the amine imide is further improved, and when the number of carbon atoms in the organic group represented by R4 is within the above range, the availability of raw materials is further improved.

[0079] Of the above, R4 in formula (1) or (2) is preferably a linear or branched alkyl group having 3 to 12 carbon atoms, or a linear or branched alkenyl group having 3 to 6 carbon atoms. The presence of such a group makes it easier to obtain a liquid amine imide that satisfies the above-mentioned viscosity, and also tends to improve the curing performance of the amine imide.

[0080] R4 in formula (3) is preferably a group represented by the following formula (9) or (10): The presence of such a group makes it easier to obtain a liquid amine imide satisfying the above-mentioned viscosity and also tends to improve the curing performance of the amine imide.

[0081] [ka]

[0082] [ka]

[0083] (In formulas (9) and (10), R 41 and R 42 each independently represents an alkyl group, an aryl group, or an aralkyl group having 1 to 5 carbon atoms, and each n independently represents an integer of 0 to 10.

[0084] The amine imide of this embodiment is represented by formula (2) or (3) above, and in formula (2) or (3), n is preferably 2 or 3, and more preferably 2. This provides the effect of improving curability.

[0085] Amine imide compositions The amine imide composition of this embodiment contains a plurality of amine imide compounds represented by formula (1), (2) or (3). The amine imide composition contains a plurality of amine imide compounds of this embodiment, since this provides an effect of improving properties from the standpoint of controlling the curing temperature or viscosity. The amine imide composition may contain a plurality of amine imide compounds having the same formula but different structures.

[0086] Particularly from the standpoint of viscosity control, amine imide compositions containing amine imides represented by formulas (1) and (3) are preferred. When multiple amine imides are contained, viscosity control tends to be easier when the content is 0.1% to 99.5% by mass of the amine imide compound represented by formula (1).

[0087] An amine imide composition containing multiple amine imides may be obtained by mixing multiple amine imides or by simultaneously producing multiple amine imides using the method for producing an amine imide described below.

[0088] Methods for Producing Amine Imide Compounds and Amine Imide Compositions There are no particular limitations on the method for producing the amine imide of this embodiment, so long as it is a method that can produce an amine imide having the above structure. Methods for producing the amine imide composition of this embodiment include mixing multiple amine imides obtained by the methods described below, and producing multiple amine imides simultaneously to obtain a mixture. An example of a method for producing an amine imide of this embodiment includes a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B), and a glycidyl ether compound (C). The manufacturing method will be described below.

[0089] The carboxylate compound (A) is not particularly limited, but examples thereof include monocarboxylate compounds and dicarboxylate compounds. Specific examples of monocarboxylate ester compounds include methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonate, methyl benzoylformate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl, etc. Alternatively, ethyl esters, propyl esters, etc. may be used. Specific examples of dicarboxylate compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate, etc. Alternatively, diethyl esters, dipropyl esters, etc. may be used.

[0090] Among these, from the viewpoints of curability and liquefaction, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate are preferred.

[0091] Among these, from the viewpoint of availability, ethyl lactate, methyl mandelate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, and diethyl 1,3-acetonedicarboxylate are more preferable. The carboxylate compound (A) may be used alone or in combination of two or more kinds.

[0092] The hydrazine compound (B) is not particularly limited, but 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.

[0093] Among these, from the viewpoint of curability and liquefaction, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred. Furthermore, among these, dibenzylhydrazine and 1-aminopiperidine are more preferred from the viewpoint of availability and safety. The hydrazine compound (B) may be used alone or in combination of two or more kinds.

[0094] The glycidyl ether compound (C) is not particularly limited, and may be, for example, a monofunctional monoglycidyl ether compound or a bifunctional or higher polyglycidyl ether compound. Specific examples of the monoglycidyl ether compound include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, orthophenylphenol glycidyl ether, benzyl glycidyl ether, biphenylyl glycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, and 3-[diethoxy(methyl)silyl]propyl glycidyl ether. Specific examples of polyglycidyl ether compounds 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, glycerin polyglycidyl ether, and the like. alicyclic polyglycidyl ether compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ethylene oxide-added bisphenol A diglycidyl ether, propylene oxide-added bisphenol A diglycidyl ether, and hydrogenated condensates thereof; and aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether.

[0095] Among these, from the viewpoints of curability and liquefaction, methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, ethylene oxide adduct-type bisphenol A diglycidyl ether, and propylene oxide adduct-type bisphenol A diglycidyl ether are preferred.

[0096] Among these, from the viewpoints of availability and Tg of the cured product, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, trimethylolpropane polyglycidyl ether, ethylene oxide-added bisphenol A diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, and propylene oxide-added bisphenol A diglycidyl ether are more preferred. The glycidyl ether compound (C) may be used alone or in combination of two or more.

[0097] The amounts of the carboxylate compound (A), the hydrazine compound (B), and the glycidyl ether compound (C) added to the reaction system can be expressed as the molar ratio of functional groups. The amount of the carboxylate group of the carboxylate compound (A) is preferably 0.8 to 3.0 mol, more preferably 0.9 to 2.8 mol, and even more preferably 0.95 to 2.5 mol, relative to 1 mol of the primary amine of the hydrazine compound (B). The amount of the glycidyl group of the glycidyl ether compound (C) is preferably 0.8 to 2.0 mol, more preferably 0.9 to 1.5 mol, and even more preferably 0.95 to 1.4 mol, relative to 1 mol of the primary amine of the hydrazine compound (B). By controlling the amount of glycidyl groups in glycidyl ether compound (C) added per mole of primary amine in hydrazine compound (B), it is possible to simultaneously prepare an amine imide composition containing amine imides of formulas (1) and (3). Specifically, the amount of glycidyl groups in glycidyl ether compound (C) added per mole of primary amine in hydrazine compound (B) is preferably 0.1 to 3.0 moles, more preferably 0.3 to 2.0 moles, and even more preferably 0.5 to 1.0 moles.

[0098] In the methods for producing amine imide compounds and amine imide compositions of this embodiment, the reaction of components (A) to (C) will proceed without the use of a solvent, but from the viewpoint of ensuring that the reaction proceeds uniformly, it is preferable to use a solvent.

[0099] The solvent is not particularly limited as long as it does not react with the components (A) to (C). Examples of the solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.

[0100] The reaction temperature is preferably 10 to 70° C., more preferably 20 to 60° C. A reaction temperature of 10° C. or higher tends to speed up the reaction and improve the purity of the resulting amine imide. A reaction temperature of 60° C. or lower efficiently inhibits polymerization reactions between glycidyl ether compounds (C), and therefore tends to improve the purity of the amine imide.

[0101] The reaction time is preferably 1 to 7 days, more preferably 1 to 6 days, and further preferably 1 to 4 days.

[0102] After completion of the reaction, the resulting reaction product can be purified by known purification methods such as washing, extraction, recrystallization, column chromatography, etc. For example, the reaction solution dissolved in an organic solvent can be washed with water and the organic layer can then be heated under normal or reduced pressure to remove unreacted raw materials and organic solvent from the reaction solution and recover the amine imide. Furthermore, the resulting reaction product can be purified by column chromatography to recover the amine imide. The solvent used for washing is not particularly limited as long as it can dissolve the residues of the raw materials. From the viewpoints of yield, purity, and ease of removal, hexane, pentane, and cyclohexane are preferred.

[0103] The organic solvent used for extraction is not particularly limited as long as it is capable of dissolving the target amine imide. From the viewpoints of yield, purity and ease of removal, preferred are ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether and methyl isobutyl ketone, and more preferred are ethyl acetate, chloroform, toluene and methyl isobutyl ketone.

[0104] As the packing material used in column chromatography, known materials such as alumina and silica gel can be used, and as the developing solvent, known materials such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, can be used alone or in combination.

[0105] [Hardening agent] The curing agent of this embodiment contains the amine imide compound or amine imide composition of this embodiment described above. The curing agent of this embodiment may contain other components in addition to the amine imide compound or amine imide composition. Examples of other components include other compounding agents such as inorganic fillers, flame retardants, core-shell rubber particles, silane coupling agents, release agents, pigments, etc. When other components are contained in addition to the amine imide compound or amine imide composition of this embodiment, the content thereof is preferably 90 mass % or less.

[0106] The amine imide of this embodiment is preferably in a liquid form at room temperature, and in such a form has excellent compatibility with epoxy resins and can be suitably used as an epoxy resin composition containing other components added thereto. The epoxy resin composition is described below.

[0107] [Epoxy resin composition] The epoxy resin composition of this embodiment contains an epoxy resin (α) and the above-described curing agent (β) of this embodiment. If necessary, the epoxy resin composition of this embodiment may further contain a curing agent other than the above-described amine imide compound and amine imide composition of this embodiment, or an optional component generally known to be used in epoxy resin compositions for various applications.

[0108] The epoxy resin (α) is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcin type epoxy resin, methylresorcin type epoxy resin, catechol type epoxy resin, N,N-diglycidylaniline type epoxy resin, ethylene oxide addition type bisphenol A type epoxy resin, bifunctional epoxy resins such as propylene oxide-added bisphenol A epoxy resins, ethylene oxide-added bisphenol F epoxy resins, and propylene oxide-added bisphenol F epoxy resins; trifunctional epoxy resins such as trisphenol epoxy resins, N,N-diglycidylaminobenzene epoxy resins, o-(N,N-diglycidylamino)toluene epoxy resins, triazine epoxy resins, ethylene oxide-added trisphenol epoxy resins, and propylene oxide-added trisphenol epoxy resins; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane epoxy resins and diaminobenzene epoxy resins; multifunctional 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 modified with isocyanates or the like can also be used in combination.

[0109] The epoxy resin composition of the present embodiment may use a curing agent other than the curing agent (β) described above. The other curing agent is not particularly limited, but may be, for example, an amine-based curing agent such as imidazoles, diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, triethylenetetramine, isophoronediamine, polyalkyleneglycolpolyamine, or a polyamide resin synthesized from a dimer of linoleic acid and ethylenediamine; an amide-based curing agent such as dicyandiamide; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, or the like. Acid anhydride-based hardeners such as water phthalic acid; phenolic hardeners such as polyhydric phenol compounds and modified products thereof, such as phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, and naphthol-cresol co-condensed novolac resin; BF3-amine complex, guanidine derivative, etc. These hardeners may be used alone or in combination of two or more.

[0110] When emphasis is placed on permeability, it is preferable to further contain an acid anhydride-based curing agent (γ) among the curing agents other than the curing agent (β).

[0111] 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) within the above range, the curing reaction is sufficiently promoted and better cured physical properties tend to be obtained.

[0112] In the epoxy resin composition of the present embodiment, when a curing agent other than the curing agent (β) is contained and the curing agent (β) is used as a curing accelerator, the content of the curing agent (β) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the total amount of the epoxy resin (α). By setting the content of the curing agent (β) as a curing accelerator within the above range, it functions as a curing catalyst for the other curing agent, sufficiently accelerates the curing reaction, and tends to obtain even better cured physical properties.

[0113] In epoxy resin compositions using a curing agent (β) containing the amine imide of this embodiment as a curing accelerator and the above-mentioned acid anhydride curing agent (γ) as a curing agent, the equivalent ratio of the acid anhydride groups of the acid anhydride curing agent (γ) to the epoxy groups of the epoxy resin (α) (acid anhydride groups / epoxy groups) is preferably 0.80 to 1.20, more preferably 0.85 to 1.15, and even more preferably 0.90 to 1.10. By setting the amounts of the epoxy resin (α) and the acid anhydride curing agent (γ) to be within the above ranges, the curing reaction is sufficiently promoted and better cured physical properties tend to be obtained.

[0114] The epoxy resin composition of the present embodiment may further contain an inorganic filler as necessary. The inorganic filler is not particularly limited, but examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, and aluminum nitride.

[0115] In the epoxy resin composition of the present embodiment, the content of the inorganic filler is not particularly limited as long as it is within a range in which the effects of the present embodiment can be obtained. In the epoxy resin composition of the present embodiment, the content of the inorganic filler is usually preferably 90 mass% or less. By setting the content of the inorganic filler within the above range, the viscosity of the epoxy resin composition tends to be sufficiently low and the handling property tends to be excellent.

[0116] The epoxy resin composition of the present embodiment may further contain other compounding agents such as a flame retardant, a silane coupling agent, a release agent, a pigment, etc., as necessary. As long as the effects of the present embodiment can be obtained, suitable compounds can be selected as appropriate. The flame retardant is not particularly limited, but examples thereof include halides, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds, etc.

[0117] [Cured product] A cured product is obtained by curing the epoxy resin composition of this embodiment. The cured product of the epoxy resin composition of this embodiment can be obtained by, for example, thermally curing the epoxy resin composition by a conventionally known method. For example, first, the above-mentioned epoxy resin, the curing agent, and, if necessary, a curing accelerator, an inorganic filler, and / or compounding agents are thoroughly mixed until homogeneous using an extruder, kneader, roll, or the like to obtain an epoxy resin composition. Thereafter, the epoxy resin composition is molded using a casting or transfer molding machine, a compression molding machine, an injection molding machine, or the like, and further heated at about 80 to 200° C. for about 2 to 10 hours to obtain a cured product.

[0118] Also, for example, a cured product can be obtained by the following method. First, the epoxy resin composition of the present embodiment is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone to obtain a solution. The obtained solution is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg. Next, the obtained prepreg is hot-press molded to obtain a cured product.

[0119] [Application] The epoxy resin composition of the present embodiment and the cured product thereof can be used in various applications in which epoxy resins are used as materials, and are particularly useful as encapsulants, encapsulants for semiconductors, adhesives, printed circuit board materials, paints, composite materials, and the like. Among these, the epoxy resin composition is preferably used in semiconductor encapsulants such as underfills and moldings, conductive adhesives such as anisotropic conductive films (ACFs), printed wiring boards such as solder resists and coverlay films, and composite materials such as prepregs obtained by impregnating glass fibers, carbon fibers, or the like with the epoxy resin composition.

[0120] (glue) The adhesive of this embodiment contains the epoxy resin composition of this embodiment described above, and the curing agent (β) preferably contains an amine imide compound represented by formula (3) above, which provides the effect of improving permeability.

[0121] (Electronic materials) The cured product of the epoxy resin composition of the present embodiment can be used for various electronic components, including, but not limited to, semiconductor encapsulants such as underfills and moldings, conductive adhesives such as ACF, printed wiring boards such as solder resists and coverlay films, and composite materials such as prepregs impregnated with glass fibers or carbon fibers. EXAMPLES

[0122] Next, the present invention will be described more specifically with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these in any way. In the following, "parts" and "%" are by weight unless otherwise specified.

[0123] Amine imides and amine imide compositions were synthesized in the Synthesis Examples described below. The physical properties of the amine imides and amine imide compositions were measured in terms of viscosity at 25° C., melting point, and infrared absorption spectrum.

[0124] [Method of measuring viscosity at 25℃] The viscosity (Pa s) of the amine imide at 25°C was measured by dropping approximately 0.3 mL of the amine imide or amine imide composition into a measuring cup and measuring the viscosity with an E-type viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.) 15 minutes after the sample temperature reached 25°C. In Table 1, "Properties" indicate the state at 25°C.

[0125] [Melt point measurement method] Melting points were measured only for those that were solid at room temperature (25° C.) The melting points of amine imide compounds and amine imide compositions were taken as the apex temperature of the endothermic peak under the following conditions: -Apparatus: Differential thermal and thermogravimetric simultaneous measurement device ("TG / DTA7220" manufactured by Hitachi High-Tech Science Corporation) Sample mass: approx. 10 mg Sample container: Open aluminum pan ·Measurement temperature: 40℃~240℃ Heating rate: 5℃ / min Atmosphere gas: Nitrogen Gas flow rate: 40mL / min

[0126] [Method for measuring NN bond decomposition temperature] The N-N bond decomposition apex temperature of an amine imide compound or an amine imide composition is the apex temperature of the exothermic peak (T peak The NN bond decomposition onset temperature was the temperature at which the exothermic peak rose (T onset ) was used. Note that the rise temperature (T onset ) was calculated from the intersection of the tangent of the maximum slope of the rising part of the exothermic peak and the extrapolated line of the baseline. peak -T onset ) was calculated. <Measurement conditions> -Apparatus: Differential thermal and thermogravimetric simultaneous measurement device ("TG / DTA7220" manufactured by Hitachi High-Tech Science Corporation) Sample mass: approx. 10 mg Sample container: Open aluminum pan ·Measurement temperature: 40℃~240℃ Heating rate: 5℃ / min Atmosphere gas: Nitrogen Gas flow rate: 40mL / min

[0127] [Method of measuring infrared absorption spectrum] 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. The liquid film method involves sandwiching a sample between rock salt plates that transmit infrared rays to create a film-like measurement sample. The tablet method involves dispersing a sample uniformly in potassium bromide powder using a mortar or other device, and then pressing the dispersion to produce a tablet-shaped measurement sample. 1570cm -1 ~1620cm -1 The presence or absence of the specific infrared absorption spectrum derived from the aminimide group seen in the compound was confirmed.

[0128] [Mass spectrometry measurement method] Mass spectrometry was performed using a Waters QDa detector as a mass spectrometry (MS) detector. The measurement sample was adjusted to a concentration of about 0.25% by mass using acetonitrile. The solution conditions were 90:10 methanol:water at the beginning, and after 3 minutes, the mixture was changed to 50:50 methanol:water. A peak was observed at about 0.1 to 0.5 minutes, and this peak was analyzed. The mass analysis conditions for the Waters QDa detector were Mass (m / z) ES+ 50-1250, capillary voltage 0.8 V, Cone voltage 25 V, and probe temperature 600°C. Each compound is H + was observed at m / z of a single charge. A 5 mM ammonium acetate / methanol solution was delivered at 0.45 mL / min to promote ionization.

[0129] Amine imide compounds and amine imide compositions were prepared as described below. The following Synthesis Examples are specific examples of amine imide compounds and amine imide compositions according to the present invention. [Synthesis Example 1] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 4 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to remove t-butyl alcohol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separatory funnel to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 44.37 g (yield 92.3%) of a pale yellow liquid amine imide compound A (compound A). The infrared absorption spectrum was measured as described above, and IR (neat): 1573 cm -1 The measured value was: m / z=401.5. Mass spectrometry revealed a peak at m / z=401.5, indicating that amine imide A, shown below, had been obtained.

[0130] [ka]

[0131] [Synthesis Example 2] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 3 days while stirring to obtain a reaction liquid. The reaction liquid obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials to obtain a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues to obtain an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 33.46 g (88.5% yield) of pale yellow viscous amine imide compound B (compound B). The infrared absorption spectrum was measured by the above method, and the results were as follows: IR (neat): 1576 cm -1 The measured value was: m / z=946.8. Mass spectrometry gave a peak at m / z=946.8, indicating that amine imide B, shown below, had been obtained.

[0132] [ka]

[0133] [Synthesis Example 3] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 4 days while stirring to obtain a reaction liquid. The reaction liquid obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials to obtain a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues to obtain an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 47.67 g (yield 94.9%) of a light brown liquid amine imide compound C (compound C). The infrared absorption spectrum was measured by the above method, and IR (neat): 1595 cm -1The measured mass was 100 nm. Mass spectrometry revealed a peak at m / z=419.5, indicating that amine imide C, shown below, had been obtained.

[0134] [ka]

[0135] [Synthesis Example 4] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 4 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues, thereby obtaining an organic layer. This 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). The infrared absorption spectrum was measured by the above method, and IR (neat): 1609 cm -1 The measured mass was 100 nm. Mass spectrometry gave a peak at m / z = 443.4, indicating that amine imide D, shown below, had been obtained.

[0136] [ka]

[0137] [Synthesis Example 5] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 3 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 33.40 g (81.5% yield) of dark brown liquid amine imide compound E (compound E). The infrared absorption spectrum was measured by the above method, and IR (neat): 1586 cm -1 The measured mass was 100 nm. Mass spectrometry gave a peak at m / z = 683.9, indicating that amine imide E, shown below, had been obtained.

[0138] [ka]

[0139] [Synthesis Example 6] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 3 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 42.51 g (yield 95.1%) of pale yellow liquid amine imide compound F (compound F). The infrared absorption spectrum was measured by the above method, and IR (neat): 1612 cm -1The measured mass was 372.5. Mass spectrometry revealed a peak at m / z=372.5, indicating that amine imide F, shown below, had been obtained.

[0140] [ka]

[0141] [Synthesis Example 7] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 4 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials to obtain a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues to obtain an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain pale yellow viscous amine imide compound G (compound G): 33.70 g (yield 89.6%). The infrared absorption spectrum was measured by the above method, and IR (neat): 1617 cm -1 Mass spectrometry gave a peak at m / z = 627.8, indicating that amine imide G, shown below, had been obtained.

[0142] [ka]

[0143] [Synthesis Example 8] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 4 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 37.54 g (yield 90.3%) of brown liquid amine imide compound H (compound H). The infrared absorption spectrum was measured by the above method, and IR (neat): 1588 cm -1 Mass spectrometry gave a peak at m / z = 347.4, indicating that amine imide H, shown below, had been obtained.

[0144] [ka]

[0145] [Synthesis Example 9] 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. This solution was reacted at 55° C. for 1 day while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 16.21 g (89.5% yield) of yellow liquid amine imide compound L (compound L). The infrared absorption spectrum was measured by the above method, and IR (neat): 1595 cm -1The measured mass was 100 nm. Mass spectrometry revealed a peak at m / z = 667.6, indicating that amine imide L, shown below, had been obtained.

[0146] [ka]

[0147] [Synthesis Example 10] 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. This solution was reacted at 55° C. for 1 day while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was repeatedly washed with hexane to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 17.07 g (yield 88.1%) of reddish-brown liquid amine imide compound M (compound M). The infrared absorption spectrum was measured by the above method, and IR (neat): 1596 cm -1 The measured mass was 100 nm. Mass spectrometry revealed a peak at m / z = 695.6, indicating that amine imide M, shown below, had been obtained.

[0148] [ka]

[0149] [Synthesis Example 11] 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. This solution was reacted at 55° C. for 1 day while stirring to obtain a reaction liquid. The reaction liquid obtained was concentrated under reduced pressure at 55° C. to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was repeatedly washed with hexane to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 19.55 g (yield 83.9%) of pale yellow liquid amine imide compound N (compound N). The infrared absorption spectrum was measured by the above method, and IR (neat): 1592 cm -1 The measured mass was 359.5. Mass spectrometry revealed a peak at m / z=359.5, indicating that amine imide N, shown below, had been obtained.

[0150] [ka]

[0151] [Synthesis Example 12] 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. This solution was reacted at 55° C. for 2 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was repeatedly washed with hexane to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 12.22 g (yield 85.7%) of pale yellow liquid amine imide compound O (compound O). The infrared absorption spectrum was measured by the above method, and IR (neat): 1592 cm -1Mass spectrometry gave a peak at m / z = 574.8, indicating that amine imide O, shown below, was obtained.

[0152] [ka]

[0153] [Synthesis Example 13] 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. This solution was reacted with stirring at 55° C. for 2 days to obtain a reaction liquid. The product was repeatedly washed with hexane to remove unreacted raw material residues, obtaining an organic layer. This organic layer was concentrated again under reduced pressure at 55° C. to obtain 12.01 g of a yellow liquid amine imide composition O2 (compound O2), which is a mixture of two types of amine imide compounds represented by the following formula. The infrared absorption spectrum was measured as described above, and IR (neat): 1593 cm -1 The measured value was 575.6 and 421.4. Mass spectrometry revealed peaks at m / z=575.6 and 421.4. The peak at m / z=575.6 has the same structure as amine imide O, and the peak at m / z=421.4 is a compound having a diol terminal on one side. This indicates that amine imide composition O2, shown below, was obtained.

[0154] [ka]

[0155] [Synthesis Example 14] A solution was obtained by mixing 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. This solution was reacted at 55° C. for 2 days with stirring to obtain a reaction liquid. The product was repeatedly washed with hexane to remove unreacted raw material residues, obtaining an organic layer. This organic layer was again concentrated under reduced pressure at 55° C. to obtain 14.56 g of a yellow liquid amine imide composition O3 (compound O3), which is a mixture of two amine imide compounds represented by the following formula. The infrared absorption spectrum was measured as described above, and IR (neat): 1592 cm -1 The measured value was 575.6 and 421.4. Mass spectrometry revealed peaks at m / z=575.6 and 421.4. The peak at m / z=575.6 has the same structure as amine imide O, and the peak at m / z=421.4 is a compound having a diol terminal on one side. This indicates that amine imide composition O3, shown below, has been obtained.

[0156] [ka]

[0157] [Synthesis Example 15] 3.64 g (0.022 mol) of methyl D,L-mandelate, 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. This solution was reacted at 55° C. for 1 day while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was repeatedly washed with hexane to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 8.41 g (yield 90.5%) of a pale yellow liquid amine imide compound P (compound P). The infrared absorption spectrum was measured by the above method, and IR (neat): 1603 cm -1The measured mass was 100 nm. Mass spectrometry revealed a peak at m / z=421.5, indicating that amine imide P, shown below, had been obtained.

[0158] [ka]

[0159] [Synthesis Example 16] 9.97 g (0.060 mol) of methyl D,L-mandelate, 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. This solution was reacted at 55° C. for 2 days with stirring to obtain a reaction liquid. The product was repeatedly washed with hexane to remove unreacted raw material residues, obtaining an organic layer. This organic layer was concentrated again under reduced pressure at 55° C. to obtain 22.76 g (87.3% yield) of a pale yellow liquid amine imide compound Q (compound Q). The infrared absorption spectrum was measured by the above-mentioned method, and IR (neat): 1603 cm -1 Mass spectrometry gave a peak at m / z = 699.7, indicating that amine imide Q, shown below, had been obtained.

[0160] [ka]

[0161] [Synthesis Example 17] 2.52 g (0.015 mol) of methyl D,L-mandelate, 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. This solution was reacted at 55° C. for 1 day with stirring to obtain a reaction liquid. The product was repeatedly washed with hexane to remove unreacted raw material residues, obtaining an organic layer. This organic layer was concentrated again under reduced pressure at 55° C. to obtain 4.91 g of a pale yellow liquid amine imide composition Q2 (compound Q2), which is a mixture of two types of amine imide compounds represented by the following formula. The infrared absorption spectrum was measured by the above-mentioned method, IR (neat): 1600 cm -1 The measured value was 699.7 and 483.4. Mass spectrometry revealed peaks at m / z=699.7 and 483.4. Peak m / z=699.7 has the same structure as amine imide Q, and peak m / z=483.4 is a compound having a diol terminal on one side. This indicates that amine imide composition Q2, shown below, was obtained.

[0162] [ka]

[0163] [Synthesis Example 18] 2.92 g (0.02 mol) of dimethyl succinate, 2.01 g (0.02 mol) of 1-aminopiperidine, 3.73 g (0.02 mol) of 2-ethylhexyl glycidyl ether, and 4.0 g (0.09 mol) of ethanol were mixed to obtain a solution. This solution was reacted at 55° C. for 1 day while stirring to obtain a reaction liquid. The reaction liquid obtained was concentrated under reduced pressure at 55° C. to distill off ethanol, by-product alcohol, and unreacted raw materials, thereby obtaining a liquid product. This product was repeatedly washed with hexane to remove unreacted raw material residues, thereby obtaining an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 4.87 g (yield 60.7%) of a pale yellow liquid amine imide compound R (compound R). The infrared absorption spectrum was measured by the above-mentioned method, and IR (neat): 1578 cm -1The measured mass was 100 nm. Mass spectrometry revealed a peak at m / z=401.5, indicating that amine imide R, shown below, had been obtained.

[0164] [ka]

[0165] [Synthesis Example 19] 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. This solution was reacted at 55° C. for one day with stirring to obtain a product. This product was repeatedly washed with hexane to remove unreacted raw material residues, obtaining an organic layer. This organic layer was concentrated again under reduced pressure at 55° C. to obtain 10.06 g (yield 81.3%) of a pale yellow liquid amine imide compound S (compound S). The infrared absorption spectrum was measured by the above-mentioned method, and IR (neat): 1578 cm -1 The measured value was: m / z=659.7. Mass spectrometry gave a peak at m / z=659.7, indicating that amine imide S, shown below, had been obtained.

[0166] [ka]

[0167] [Synthesis Example 20] 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. This solution was reacted at 55° C. for one day with stirring to obtain a product. This product was repeatedly washed with hexane to remove unreacted raw material residues, obtaining an organic layer. This organic layer was concentrated again under reduced pressure at 55° C. to obtain 8.31 g of a pale yellow liquid amine imide composition S2 (compound S2), which is a mixture of two types of amine imide compounds represented by the following formula. The infrared absorption spectrum was measured as described above, and IR (neat): 1578 cm -1 The measured value was 659.6 and 477.5. Mass spectrometry revealed peaks at m / z=659.6 and 477.5. Peak m / z=659.6 has the same structure as amine imide O, and peak m / z=477.5 is a compound having a diol terminal on one side. This indicates that amine imide composition S2, shown below, was obtained.

[0168] [ka]

[0169] [Synthesis Example 21] 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. This solution was reacted at 55° C. for one day with stirring to obtain a product. This product was repeatedly washed with hexane to remove unreacted raw material residues, obtaining an organic layer. This organic layer was concentrated again under reduced pressure at 55° C. to obtain 7.31 g of a pale yellow liquid amine imide composition S3 (compound S3), which is a mixture of two types of amine imide compounds represented by the following formula. The infrared absorption spectrum was measured as described above, and IR (neat): 1578 cm -1The measured value was 659.6 and 477.5. Mass spectrometry revealed peaks at m / z=659.6 and 477.5. Peak m / z=659.6 has the same structure as amine imide O, and peak m / z=477.5 is a compound having a diol terminal on one side. This indicates that amine imide composition S3, shown below, was obtained.

[0170] [ka]

[0171] [Synthesis Example 22] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 3 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials to obtain a solid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues to obtain an organic layer. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 29.14 g (84.8% yield) of pale yellow crystalline solid amine imide compound I (compound I). The infrared absorption spectrum was measured by the above method, and the results were as follows: IR (KBr): 1592 cm -1 The measured mass was 100 nm. Mass spectrometry revealed a peak at m / z=287.4, indicating that amine imide I, shown below, had been obtained.

[0172] [ka]

[0173] [Synthesis Example 23] 19.94 g (0.12 mol) of methyl DL-mandelate, 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 4 days with stirring to obtain a reaction solution. The reaction solution was concentrated under reduced pressure at 55° C. to remove t-butyl alcohol, by-product alcohol, and unreacted raw materials, thereby obtaining a solid product. This product was recrystallized using ethyl acetate to obtain 30.11 g (72.0% yield) of white crystalline solid amine imide compound J (compound J). The infrared absorption spectrum was measured by the above method, and the results were as follows: IR(KBr): 1594 cm -1 Mass spectrometry gave a peak at m / z = 349.3, indicating that amine imide J, shown below, had been obtained.

[0174] [ka]

[0175] [Synthesis Example 24] 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 t-butyl alcohol were mixed to obtain a solution. This solution was reacted at 55° C. for 4 days while stirring to obtain a reaction solution. The reaction solution obtained was concentrated under reduced pressure at 55° C. to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials, thereby obtaining a solid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separating funnel to remove unreacted raw material residues. This organic layer was concentrated under reduced pressure again at 55° C. to obtain 33.05 g (84.1% yield) of white non-crystalline solid amine imide compound K (compound K). The infrared absorption spectrum was measured by the above method, and the results were as follows: IR (KBr): 1570 cm -1The measured value was: m / z=655.8. Mass spectrometry gave a peak at m / z=655.8, indicating that amine imide K, shown below, had been obtained.

[0176] [ka]

[0177] [Comparative Synthesis Example 1] 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. This solution was reacted at 120° C. for 4 hours while stirring to obtain a liquid product. This product was dissolved in ethyl acetate and repeatedly washed with water in a separatory funnel to remove unreacted raw materials, obtaining an organic layer. This 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. A peak of m / z=294.4 was observed in mass spectrometry.

[0178] [ka]

[0179] The evaluation results of Synthesis Examples 1 to 24 and Comparative Synthesis Example 1 are shown in Table 1 below.

[0180] [Table 1]

[0181] Next, epoxy resin compositions were prepared containing the amine imide compounds and amine imide compositions of [Synthesis Examples 1-24] and the acrylate-imidazole adduct of [Comparative Synthesis Example 1] as a curing agent. The various properties of this epoxy resin composition, such as curability and storage stability at room temperature (25° C.), were measured.

[0182] [Preparation of epoxy resin composition (1)] The epoxy resin compositions prepared in the following Examples and Comparative Examples were prepared using the following epoxy resins as raw materials. Epoxy resin: Chang Chun Plastics Co., Ltd "BE-186EL"

[0183] When mixing the raw materials, 2 to 20 parts by mass of the amine imide, amine imide composition, or acrylate-imidazole adduct were added per 100 parts by mass of epoxy resin. The epoxy resin and the amine imide, amine imide composition, or acrylate-imidazole adduct were placed in a plastic stirring vessel and stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation) to prepare an epoxy resin composition.

[0184] [Cure evaluation method (1)] In the evaluation method (1) of curability, 10 mg of the prepared epoxy resin composition was weighed out and placed in an aluminum container of a differential scanning calorimeter (manufactured by SII Corporation, "DSC220C"), heated in an oven at 200°C for 3 hours, and then rapidly cooled. The reaction rate was calculated from the change in the DSC heat generation rate before and after heating, and the curability was evaluated based on this reaction rate. A response rate of 95% or more was judged as "◎", a response rate of 90% or more but less than 95% was judged as "○", a response rate of 80% or more but less than 90% was judged as "△", and a response rate of less than 80% was judged as "×".

[0185] [Evaluation method for storage stability (1)] In the evaluation method (1) of storage stability, the viscosity of the epoxy resin composition immediately after preparation at 25°C was defined as "η1", and the viscosity of the epoxy resin composition stored in a thermostatic bath at 25°C for 3 days was defined as "η2", and the value calculated by η2 / η1 was determined as the viscosity increase ratio, and the storage stability at room temperature was evaluated based on this viscosity increase ratio. A viscosity increase rate of less than 1.5 times was judged as "◎", a viscosity increase rate of 1.5 to less than 2.0 times was judged as "○", a viscosity increase rate of 2.0 to less than 3.0 times was judged as "△", and a viscosity increase rate of 3.0 times or more was judged as "X".

[0186] [Example 1] An epoxy resin composition was prepared by placing 20 g of epoxy resin ("BE-186EL" manufactured by Chang Chun Plastics Co., Ltd.) and 1.6 g of amine imide compound A in a plastic stirring vessel and stirring and mixing the mixture using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation). The curability was evaluated according to the above-mentioned method for evaluating curability (1), and the storage stability at room temperature was evaluated according to the above-mentioned method for evaluating storage stability (1).

[0187] [Example 2] An epoxy resin composition was prepared in the same manner as in Example 1, except that the amount of amine imide A added was changed to 6.0 g, and its curability and storage stability at room temperature were evaluated.

[0188] [Example 3] An epoxy resin composition was prepared as in Example 1, except that amine imide A was changed to amine imide B and the amount of amine imide B added was changed to 2.0 g, and the curability and storage stability at room temperature were evaluated.

[0189] [Example 4] An epoxy resin composition was prepared as in Example 1, except that amine imide A was changed to amine imide C and the amount of amine imide C added was changed to 6.0 g, and then its curability and storage stability at room temperature were evaluated.

[0190] [Example 5] An epoxy resin composition was prepared as in Example 1, except that amine imide A was changed to amine imide C and the amount of amine imide C added was changed to 0.4 g, and the curability and storage stability at room temperature were evaluated.

[0191] [Example 6] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was changed to amine imide C, and the curability and storage stability at room temperature were evaluated.

[0192] [Example 7] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide compound D was used instead of amine imide compound A, and its curability and storage stability at room temperature were evaluated.

[0193] [Example 8] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide compound E was used instead of amine imide compound A, and its curability and storage stability at room temperature were evaluated.

[0194] [Example 9] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide F, and the curability and storage stability at room temperature were evaluated.

[0195] [Example 10] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide G, and the curability and storage stability at room temperature were evaluated.

[0196] [Example 11] An epoxy resin composition was prepared in the same manner as in Example 5, except that amine imide C was replaced with amine imide H, and the curability and storage stability at room temperature were evaluated.

[0197] [Example 12] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide H, and the curability and storage stability at room temperature were evaluated.

[0198] [Example 13] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide L, and the curability and storage stability at room temperature were evaluated.

[0199] [Example 14] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide M, and the curability and storage stability at room temperature were evaluated.

[0200] [Example 15] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide N, and the curability and storage stability at room temperature were evaluated.

[0201] [Example 16] An epoxy resin composition was prepared in the same manner as in Example 2, except that amine imide A was replaced with amine imide N, and the curability and storage stability at room temperature were evaluated.

[0202] [Example 17] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide O, and the curability and storage stability at room temperature were evaluated.

[0203] [Example 18] An epoxy resin composition was prepared in the same manner as in Example 2, except that amine imide A was replaced with amine imide O, and the curability and storage stability at room temperature were evaluated.

[0204] [Example 19] An epoxy resin composition was prepared as in Example 1, except that amine imide compound A was replaced with amine imide composition O2, and its curability and storage stability at room temperature were evaluated.

[0205] [Example 20] An epoxy resin composition was prepared as in Example 1, except that amine imide compound A was replaced with amine imide composition O3, and its curability and storage stability at room temperature were evaluated.

[0206] [Example 21] An epoxy resin composition was prepared as in Example 2, except that amine imide compound A was replaced with amine imide composition O3, and its curability and storage stability at room temperature were evaluated.

[0207] [Example 22] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide P, and the curability and storage stability at room temperature were evaluated.

[0208] [Example 23] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide Q, and the curability and storage stability at room temperature were evaluated.

[0209] [Example 24] An epoxy resin composition was prepared as in Example 1, except that Amine imide Compound A was replaced with Amine imide Composition Q2, and its curability and storage stability at room temperature were evaluated.

[0210] [Example 25] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide R, and the curability and storage stability at room temperature were evaluated.

[0211] [Example 26] An epoxy resin composition was prepared in the same manner as in Example 2, except that amine imide compound R was used instead of amine imide compound A, and its curability and storage stability at room temperature were evaluated.

[0212] [Example 27] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide compound S was used instead of amine imide compound A, and its curability and storage stability at room temperature were evaluated.

[0213] [Example 28] An epoxy resin composition was prepared in the same manner as in Example 2, except that amine imide compound S was used instead of amine imide compound A, and its curability and storage stability at room temperature were evaluated.

[0214] [Example 29] An epoxy resin composition was prepared as in Example 1, except that Amine imide Compound A was replaced with Amine imide Composition S2, and the curability and storage stability at room temperature were evaluated.

[0215] [Example 30] An epoxy resin composition was prepared as in Example 2, except that Amine imide Compound A was replaced with Amine imide Composition S2, and the curability and storage stability at room temperature were evaluated.

[0216] [Example 31] An epoxy resin composition was prepared as in Example 2, except that Amine imide Compound A was replaced with Amine imide Composition S3, and its curability and storage stability at room temperature were evaluated.

[0217] [Example 59] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide I was used instead of amine imide A, and its curability and storage stability at room temperature were evaluated.

[0218] [Example 60] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide J, and the curability and storage stability at room temperature were evaluated.

[0219] [Example 61] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was replaced with amine imide K, and the curability and storage stability at room temperature were evaluated.

[0220] [Comparative Example 1] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was changed to DBU (Tokyo Chemical Industry Co., Ltd., "diazabicycloundecene"), and the curability and storage stability at room temperature were evaluated.

[0221] [Comparative Example 2] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was changed to DBU-phenol salt ("U-CAT SA1" manufactured by San-Apro Ltd.), and the curability and storage stability at room temperature were evaluated.

[0222] [Comparative Example 3] An epoxy resin composition was prepared in the same manner as in Example 1, except that amine imide A was changed to an acrylate-imidazole adduct, and the curability and storage stability at room temperature were evaluated.

[0223] The evaluation results of Examples 1 to 31, 59 to 61 and Comparative Examples 1 to 3 are shown in Tables 2 to 6.

[0224] [Table 2]

[0225] [Table 3]

[0226] [Table 4]

[0227] [Table 5]

[0228] [Table 6]

[0229] [Preparation of epoxy resin composition (2)] The epoxy resin compositions prepared in the following Examples and Comparative Examples were prepared using the following epoxy resins and acid anhydrides as raw materials. Epoxy resin: Chang Chun Plastics Co., Ltd "BE-186EL" Acid anhydride: Hitachi Chemical Co., Ltd. "HN-5500"

[0230] The raw materials were mixed so that the equivalent ratio of the epoxy groups in the epoxy resin and the acid anhydride groups in the acid anhydride was acid anhydride groups / epoxy groups=1.00. Furthermore, each raw material was added according to the blending amounts shown in Tables 7 to 9 relative to 100 parts by mass of the epoxy resin. An epoxy resin and an amine imide, an amine imide composition, DBU, U-CAT SA1, or an acrylate-imidazole adduct (hereinafter sometimes referred to as an amine imide, etc.) were placed in a plastic stirring vessel and stirred and mixed using a planetary centrifugal mixer (ARE-310, manufactured by Thinky Corporation) to pre-mix the epoxy resin and the amine imide, etc. A predetermined amount of an acid anhydride was then added to the pre-mixture, which was then further stirred and mixed to prepare an epoxy resin composition.

[0231] [Cure evaluation method (2)] For evaluation method (2) of curability, the prepared epoxy resin composition was heated under the following conditions and evaluated. When the temperature reached 100 Pa s was less than +15°C compared to when DBU was used as the curing accelerator, it was judged as "◎", when it was +15 to less than +30°C, it was judged as "○", when it was +30 to less than +45°C, it was judged as "△", and when it was +45°C or more, it was judged as "×". <Measurement conditions> Equipment: Viscoelasticity measuring device ("HAAKE MARS" manufactured by ThermoScientific) Sample mass: approx. 0.5 mL Plate shape: Parallel Measurement mode: constant shear rate (dγ / dt=1.0s -1 ) ·Measurement temperature: 40℃~240℃ Heating rate: 5℃ / min

[0232] [Evaluation method for storage stability (2)] In the evaluation method (2) for storage stability, the viscosity at 25°C of the epoxy resin composition immediately after preparation was taken as "η1", and the viscosity at 25°C of the epoxy resin composition stored in a thermostatic bath at 25°C for 3 days was taken as "η2", and the value calculated from η2 / η1 was determined as the viscosity increase ratio. A viscosity increase ratio of less than 3.0 times was judged as "◎", a viscosity increase ratio of 3.0 times or more and less than 7.0 times was judged as "○", a viscosity increase ratio of 7.0 times or more and less than 10.0 times was judged as "△", and a viscosity increase ratio of 10.0 times or more was judged as "X".

[0233] [Prepreg surface smoothness evaluation method] The prepared epoxy resin composition was applied to a carbon fiber cloth ("TORAYCA CLOTH CO6343" manufactured by Toray Industries, Inc.) (basis weight 198 g / m 2 ) for 5 minutes and heated in an oven at 170°C for 10 minutes to produce a prepreg. The surface condition of the obtained prepreg was then observed. Those with a smooth surface were judged as "○", and those with unevenness due to voids or the like were judged as "×".

[0234] [Evaluation method for prepreg tackiness] The prepared epoxy resin composition was applied to a carbon fiber cloth ("TORAYCA CLOTH CO6343" manufactured by Toray Industries, Inc.) (basis weight 198 g / m 2 The prepreg was then impregnated with 170°C water for 5 minutes and heated in an oven at 170°C for 10 minutes to produce a prepreg. The tackiness of the resulting prepreg was then checked. Those with no tackiness were rated as "○" and those with tackiness were rated as "×".

[0235] [Method of evaluating permeability] The pressurized filter was fitted with a carbon fiber cloth (Toray Industries, Inc.'s "TORAYCA CLOTH CO6343") (weight 198 g / m 2 ) was sandwiched between two plates, and the prepared epoxy resin composition was pressure-filtered with nitrogen at 0.2 L / min at room temperature. 10 mg of the epoxy resin composition obtained as the filtrate was weighed out and placed in an aluminum container of a differential scanning calorimeter ("DSC220C" manufactured by SII Corporation), heated in an oven at 180°C for 1.5 hours, and then rapidly cooled. The reaction rate was calculated from the change in the DSC calorific value before and after filtration. A reaction rate of 95% or more was judged as "○", and a reaction rate of less than 95% was judged as "×".

[0236] In this evaluation, it was confirmed that when an amine imide compound or the like is used as a curing accelerator, if the curing accelerator has excellent permeability, there is no difference in the amount of curing accelerator in the epoxy resin composition before and after pressure filtration, and the desired reactivity is obtained. On the other hand, it was confirmed that if the curing accelerator has poor permeability, at least a portion of the curing accelerator is trapped in the carbon fiber cloth, reducing the amount of curing accelerator in the epoxy resin composition after pressure filtration, resulting in the desired reactivity not being obtained.

[0237] [Example 32] 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 vessel and stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation). 17.9 g of acid anhydride ("HN-5500" manufactured by Hitachi Chemical Co., Ltd.) was then added and further stirred and mixed to prepare an epoxy resin composition. The curability was evaluated by the above-mentioned evaluation method for curability (2), the storage stability at room temperature was evaluated by the above-mentioned evaluation method for storage stability (2), and the prepreg surface smoothness, prepreg tackiness, and permeability were also evaluated.

[0238] [Example 33] An epoxy resin composition was prepared in the same manner as in Example 32, except that the amount of amine imide A added was changed to 3.6 g, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0239] [Example 34] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide B, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0240] [Example 35] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide B and the amount of amine imide B added was changed to 3.6 g, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness and permeability were evaluated.

[0241] [Example 36] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide B and the amount of amine imide B added was changed to 4.8 g, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness and permeability were evaluated.

[0242] [Example 37] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide C and the amount of amine imide C added was changed to 0.2 g, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness and permeability were evaluated.

[0243] [Example 38] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide C, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0244] [Example 39] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide D, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0245] [Example 40] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide E, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0246] [Example 41] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide F, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0247] [Example 42] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide F and the amount of amine imide F added was changed to 2.0 g, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness and permeability were evaluated.

[0248] [Example 43] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide G, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0249] [Example 44] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide H and the amount of amine imide H added was changed to 0.2 g, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness and permeability were evaluated.

[0250] [Example 45] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide H, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0251] [Example 46] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide L, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0252] [Example 47] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide M, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0253] [Example 48] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide N, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0254] [Example 49] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide O, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0255] [Example 50] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was replaced with amine imide composition O2, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0256] [Example 51] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was replaced with amine imide composition O3, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0257] [Example 52] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide P, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0258] [Example 53] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide Q, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0259] [Example 54] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide composition Q2, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0260] [Example 55] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide R, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0261] [Example 56] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide S, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0262] [Example 57] An epoxy resin composition was prepared in the same manner as in Example 32, except that Amine imide A was changed to Amine imide composition S2, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0263] [Example 58] An epoxy resin composition was prepared in the same manner as in Example 32, except that Amine imide A was changed to Amine imide composition S3, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0264] [Example 62] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide I, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0265] [Example 63] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide J, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0266] [Example 64] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to amine imide K, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0267] [Comparative Example 4] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide 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 tackiness, and permeability were evaluated.

[0268] [Comparative Example 5] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to DBU-phenol salt ("U-CAT SA1" manufactured by San-Apro Ltd.), and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0269] [Comparative Example 6] An epoxy resin composition was prepared in the same manner as in Example 32, except that amine imide A was changed to acrylate-imidazole adduct A, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0270] [Comparative Example 7] An epoxy resin composition was prepared in the same manner as in Example 32, except that a powdered amine curing agent (Amicure PN-23, manufactured by Ajinomoto Fine-Techno Co., Inc.) was used instead of amine imide A, and the curability, storage stability at room temperature, prepreg surface smoothness, prepreg tackiness, and permeability were evaluated.

[0271] The evaluation results of Examples 32 to 58, 62 to 64 and Comparative Examples 4 to 7 are shown in Tables 7 to 9.

[0272] [Table 7]

[0273] [Table 8]

[0274] [Table 9]

[0275] The results in Tables 1-9 confirm that the epoxy resin compositions of Examples 1-64, which used the amine imide compounds obtained in Synthesis Examples 1-24 or amine imide compositions A-S3, exhibit excellent curability and storage stability.

[0276] The results in Tables 7 to 9 also demonstrate that the epoxy resin compositions of Examples 32 to 64, which used the amine imides or amine imide compositions A to S3 obtained in Preparative Examples 1 to 24, also exhibit excellent permeability and exhibit good prepreg properties.

[0277] On the other hand, it was confirmed that the epoxy resin compositions of Comparative Examples 1 to 7 had excellent curability but poor storage stability at room temperature.

[0278] [Method of measuring shear adhesive strength] The tensile shear adhesive strength to steel plates was measured in accordance with JIS K6850. The shear adhesion evaluation was carried out using the epoxy resin compositions of Examples 65 to 68 prepared as follows.

[0279] [Examples 65 to 76] As the epoxy resins for 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 epoxy resin "jER630" manufactured by Mitsubishi Chemical Corporation, and naphthalene type epoxy resin: "HP-4032D" manufactured by DIC Corporation were used. A specific amine imide shown in Table 10 below was added in an amount of 20 parts by mass per 100 parts by mass of total epoxy resin. Acrylate-imidazole was added in an amount of 10 parts by mass. The epoxy resin and amine imide were placed in a plastic stirring vessel and stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation) to prepare an epoxy resin composition. The epoxy resin composition prepared as described above was applied between two steel plate test pieces (SPCC-SB: manufactured by Standard Test Piece Co., Ltd.) with an adhesive area of ​​12.5 mm x 5 mm, and then heated in a heating furnace at a set temperature of 150°C for 2 hours to heat-cure and bond the test pieces to obtain test pieces. The tensile shear adhesive strength of the test pieces obtained was measured using an AUTOGRAPH AGS-X 5kN (manufactured by Shimadzu Corporation) in a constant temperature and humidity room at 23°C and 50% RH, and the median of the obtained values ​​was taken as the tensile shear adhesive strength to the steel plate substrate.

[0280] [Table 10]

[0281] From the measurement results shown in Table 10, -N - -N + Structures having multiple -NN- groups (e.g., amine imide compounds O and M) have almost the same -NN- decomposition temperatures (onset temperature, peak temperature). - -N +The shear adhesive strength was found to be higher under the same curing conditions than that of the one with only one -N in one molecule. - -N + This is believed to be due to the fact that when there are multiple - groups, the amount of active ingredient in the hardener mass increases.

[0282] This application is based on a Japanese patent application (Patent Application No. 2020-121122) filed with the Japan Patent Office on July 15, 2020, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0283] The amine imide compounds and epoxy resin compositions of the present invention have industrial applicability as, for example, encapsulants, adhesives, printed circuit board materials, paints, composite materials, semiconductor encapsulants such as underfills and moldings, conductive adhesives such as ACF, printed wiring boards such as solder resists and coverlay films, and composite materials such as prepregs impregnated with glass fibers or carbon fibers.

Claims

1. An amine imide compound represented by the following formula (1), (2) or (3): 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 (In formulas (1) to (3), R 1 each independently represents a hydrogen atom, or a monovalent or n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R 2 and R 3 each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or R 2 and R 3 represents a heterocycle having 7 or less carbon atoms to which R is linked; 4 each independently represents a monovalent or n-valent organic group having 1 to 30 carbon atoms which may contain a hydrogen atom or an oxygen atom, and n represents an integer of 1 to 3.

2. The R in the formula (1) or (3) 1 is a group represented by the following formula (4) or (5): The amine imide compound of claim 1. 【Chemistry 4】 【Chemistry 5】 (In formulas (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 each n independently represents an integer of 0 to 6.

3. The R in the formula (2) 1 is a group represented by the following formula (6) or (7): The amine imide compound of claim 1. 【Chemistry 6】 【Chemistry 7】 (In formulas (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.

4. R 2 and R 3 At least one of the groups represents an aralkyl group. The amine imide compound according to claim 1 .

5. R 2 and R 3 is a heterocycle having 7 or less carbon atoms to which R is linked, represented by the following formula (8): 23 and N in formula (1), (2) or (3) + is a heterocycle formed by The amine imide compound according to claim 1 . 【Chemistry 8】 (In formula (8), R 23 is N + represents a group which, together with

6. The R in the formula (1) or (2) 4 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; The amine imide compound according to claim 1 .

7. The R in the formula (3) 4 is a group represented by the following formula (9) or (10): The amine imide compound according to claim 1 . 【Chemistry 9】 【Chemistry 10】 (In formulas (9) and (10), R 41 and R 42 each independently represents an alkyl group, an aryl group, or an aralkyl group having 1 to 5 carbon atoms, and each n independently represents an integer of 0 to 10.

8. the amine imide compound is represented by formula (2) or (3), wherein n is 2 or 3; The amine imide compound according to claim 1 .

9. the amine imide compound is represented by formula (2) or (3), wherein n is 2; The amine imide compound according to claim 1 .

10. The viscosity at 25°C is 1300 Pa s or less. The amine imide compound according to claim 1 .

11. The top temperature of the exothermic peak associated with the decomposition of the N-N bond in differential thermal analysis (T peak ) and rise temperature (T onset ) and the difference (T peak -T onset ) is 45° C. or less; 11. The amine imide compound of claim 1.

12. 12. An amine imide composition comprising a plurality of amine imide compounds according to any one of claims 1 to 11.

13. 13. The amine imide composition of claim 12, comprising amine imide compounds represented by formula (1) and formula (3).

14. 14. A curing agent comprising the amine imide compound of claim 1 or the amine imide composition of claim 12.

15. An epoxy resin (α), A curing agent (β) according to claim 14; , including, Epoxy resin composition.

16. 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). The epoxy resin composition according to claim 15.

17. Further containing an acid anhydride-based curing agent (γ), 17. The epoxy resin composition according to claim 15 or 16.

18. 14. A method for producing an amine imide according to any one of claims 1 to 11 or in an amine imide composition according to claim 12 or 13, comprising the steps of: The method includes a reaction step of reacting a carboxylate compound (A), a hydrazine compound (B), and a glycidyl ether compound (C), Method for producing amine imides.

19. An encapsulant comprising a cured product of the epoxy resin composition according to any one of claims 15 to 17.

20. The epoxy resin composition according to claim 15, The adhesive wherein the curing agent (β) comprises an amine imide compound represented by formula (3).

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