Epoxy resin compositions, cured products, sealants, and adhesives

Abstract

An epoxy resin composition comprising (A) an epoxy resin and (B) a curing agent having heteroatoms, wherein the molecular weight α of the curing agent having heteroatoms (B) is 200 ≤ α ≤ 1200, and the value of the ratio α / β of the molecular weight α to the number of heteroatoms β in the structure of the curing agent having heteroatoms (B) is 30 ≤ α / β ≤ 95.

Description

Technology Field

[0001] The present invention relates to an epoxy resin composition, a cured product, a sealant, and an adhesive. Background Technology

[0002] Epoxy resins are widely used in applications such as paints, electrical and electronic insulating materials, and adhesives, as their cured products possess excellent performance in terms of mechanical, electrical, thermal, chemical resistance, and adhesion.

[0003] Patent Document 1 below discloses a resin used in semiconductor packages. The epoxy resin composition currently in general use is a so-called two-component epoxy resin composition in which the epoxy resin and a curing agent are mixed at the time of use.

[0004] While two-component epoxy resin compositions can be cured at room temperature, storage and handling are cumbersome because the epoxy resin and the curing agent must be stored separately and then weighed and mixed as needed. Furthermore, since the usable time is limited, it cannot be mixed in large quantities in advance, which increases the frequency of mixing and inevitably leads to a decrease in efficiency.

[0005] To solve the problems of such two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed so far. For example, an epoxy resin composition in which a latent curing agent is blended into the epoxy resin can be cited. Patent Document 2 discloses an epoxy resin composition using liquid aromatic amines.

[0006] Furthermore, the demands for electronic devices these days extend across various fields, including miniaturization, high functionality, lightweighting, and multifunctionality. For example, in semiconductor chip mounting technology, there is a demand for miniaturization, miniaturization, and high density of the single layer through fine pitching of electrode pads and pad pitches. Additionally, underfill is used as an adhesive to protect the bump connection area and the circuit surface of the chip in the gap between the chip and the substrate. However, with the fine pitching, there is a demand for underfill that penetrates into narrower gaps and exhibits good adhesion. Prior art literature

[0007] Japanese Patent Publication No. 6282515 and Japanese Patent Publication No. 2019-172738 The problem to be solved

[0008] As described above, the latent curing agent constituting the one-component epoxy resin composition requires good curing performance and storage stability after mixing with the epoxy resin, and furthermore, good penetration and adhesion are required between the narrow gap areas of electronic components and between dense fibers such as carbon fibers or glass fibers.

[0009] Patent Document 1 discloses a resin composition using an aromatic amine compound as a curing agent, but the curing agent used is solid and has the problem that it is difficult to penetrate into narrow gaps.

[0010] Patent Document 2 discloses an epoxy resin composition using a liquid aromatic amine compound as a curing agent, but it has the problem that storage and handling are cumbersome because it is necessary to add additives to improve the storage stability and adhesion of the curing agent.

[0011] Therefore, the present invention aims to provide an epoxy resin composition having good adhesive properties, a cured product of the epoxy resin composition, a sealant, and an adhesive, taking into account the circumstances described above. means of solving the problem

[0012] As a result of careful consideration to solve the above-mentioned problem, the inventors discovered that an epoxy resin composition comprising a specific curing agent and having the molecular weight of the curing agent and the number of heteroatoms in the structure within a specific range can solve the above-mentioned problem, and thus completed the present invention.

[0013] That is, the present invention is as follows.

[0014] [1]

[0015] (A) Epoxy resin and,

[0016] (B) Curing agent having heteroatoms

[0017] Contains,

[0018] The molecular weight α of the curing agent having the above (B) heteroatom is 200≤α≤1200, and

[0019] A curing agent having the above molecular weight α and the above (B) heteroatom, wherein the ratio α / β of the number of heteroatoms β in the structure of the above curing agent is 30≤α / β≤95

[0020] Epoxy resin composition.

[0021] [2]

[0022] The above epoxy resin composition described in [1], wherein the curing agent having the above (B) heteroatom comprises an amineimide compound represented by the following formula (1), formula (2), or formula (3).

[0023]

[0024] (In formulas (1) to (3), R1 each independently represents a monovalent or n-valent organic group having 1 to 15 carbon atoms, which may have a hydrogen atom, or a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 each independently represent an unsubstituted or substituent alkyl group, an aryl group, an aralkyl group having 1 to 12 carbon atoms, or a heterocyclic group having 7 or fewer carbon atoms connected by R2 and R3; R4 each independently represents a monovalent or n-valent organic group having 1 to 30 carbon atoms, which may include a hydrogen atom or an oxygen atom; and n represents an integer from 1 to 3.)

[0025] [3]

[0026] An epoxy resin composition described in [2], wherein n in the above formula (2) or the above formula (3) is 2 or 3.

[0027] [4]

[0028] An epoxy resin composition described in any one of [1] to [3], comprising (C) an inorganic filler.

[0029] [5]

[0030] The epoxy resin composition described in [4], wherein the content of the inorganic filler (C) above is greater than 5 mass% and less than or equal to 98 mass% with respect to the entire epoxy resin composition.

[0031] [6]

[0032] An epoxy resin composition described in any one of [1] to [5], comprising (D) a stabilizer.

[0033] [7]

[0034] The epoxy resin composition described in [6], wherein the above (D) stabilizer comprises a compound represented by the following formula (A) or (B).

[0035]

[0036] (In formula (A), R5 and R6 each independently represent a monovalent or n-valent organic group having 1 to 15 carbon atoms, which may have a hydrogen atom, or a hydroxyl group, a carbonyl group, an ester bond, or an ether bond, and n represents an integer from 2 to 3.)

[0037]

[0038] (In formula (B), R7 represents 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, and n represents an integer from 2 to 3.)

[0039] [8]

[0040] The content of the above (D) stabilizer is, with respect to 100 parts by mass of the above (A) epoxy resin,

[0041] An epoxy resin composition as described in [6] or [7], having an amount of 1 part by mass or more and 30 parts by mass or less.

[0042] [9]

[0043] A cured product of the epoxy resin composition described in any one of [1] to [8] above.

[0044]

[10]

[0045] A sealant comprising the cured material described in [9] above.

[0046]

[11]

[0047] The sealing material described in

[10] above, which is a sealing material for semiconductors.

[0048]

[12]

[0049] An adhesive comprising the epoxy resin composition described in any one of [1] to [8] above. Effects of the invention

[0050] According to the present invention, an epoxy resin composition having good adhesion, a cured product of the epoxy resin composition, a sealant, and an adhesive can be provided. Specific details for implementing the invention

[0051] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. Furthermore, the present embodiment is an example for explaining the present invention and is not intended to limit the present invention to the contents below, and the present invention may be carried out with various modifications within the scope of its gist.

[0052] [Epoxy resin composition]

[0053] The epoxy resin composition of the present embodiment is,

[0054] (A) Epoxy resin and,

[0055] (B) A curing agent having heteroatoms (hereinafter referred to as (B) curing agent) is contained, and the molecular weight α of the curing agent having heteroatoms (hereinafter referred to simply as "molecular weight α") is 200≤α≤1200, and the ratio α / β of the number of heteroatoms β in the structure of the curing agent having heteroatoms (hereinafter referred to simply as "number of heteroatoms β") is 30≤α / β≤95.

[0056] The epoxy resin composition of the present embodiment has excellent adhesion by having the above-described composition. The factors for this may be considered as follows, but are not limited to these.

[0057] That is, it is believed that since the molecular weight α of the curing agent having (B) heteroatoms is 200 or more, the crosslinking length during curing is increased and a tough structure is obtained, so the cohesive failure of the cured product can be suppressed and the adhesion is improved. On the other hand, since the molecular weight α of the curing agent having (B) heteroatoms is 1200 or less, the curing agent (B) has excellent dispersibility and can be sufficiently dispersed in the (A) epoxy resin and exhibit sufficient curability, and as a result, sufficient adhesion is obtained.

[0058] In addition, it is believed that when the value of the ratio α / β, which includes the molecular weight α and the number of heteroatoms β in the structure of the curing agent (B), is 95 or less, the number of polar functional groups in the curing agent having the heteroatoms (B) increases, and the epoxy resin composition of the present embodiment and the substrate adhere firmly through intermolecular bonding. On the other hand, when the ratio α / β of the molecular weight α and the number of heteroatoms β in the structure of the curing agent having the heteroatoms (B) is 30 or more, the compatibility between the curing agent (B) and the epoxy resin (A) increases, and the epoxy resin composition can be sufficiently cured, so it is believed that sufficient adhesion can be obtained as a result.

[0059] In the epoxy resin composition of the present embodiment, the lower limit of the molecular weight α of the curing agent having (B) heteroatoms is 200 or higher, preferably 220 or higher, and more preferably 250 or higher. The upper limit of the molecular weight α of the curing agent including (B) heteroatoms is 1200 or lower, preferably 1100 or lower, more preferably 1000 or lower, and even more preferably 900.

[0060] In addition, (B) the molecular weight α of the curing agent having heteroatoms can be measured using a mass spectrometer (ESI-MS).

[0061] In the epoxy resin composition of the present embodiment, the lower limit of the value of the ratio α / β of the molecular weight α and the number of heteroatoms β in the structure of the curing agent having the (B) heteroatom is 30 or higher, preferably 35 or higher, and more preferably 40 or higher. The upper limit of the value of the ratio α / β is 95 or lower, preferably 90 or lower, and more preferably 80 or lower.

[0062] The number of heteroatoms β in the structure of the curing agent having the above (B) heteroatoms can be measured by a mass spectrometer (ESI-MS).

[0063] (B) The number of heteroatoms β in the structure of the curing agent having heteroatoms is not particularly limited, but (A) from the perspective of compatibility with the epoxy resin, it is preferred to be 5 or more and 25 or less, more preferred to be 5 or more and 20 or less, and even more preferred to be 5 or more and 15 or less.

[0064] (B) In the process of preparing a curing agent having heteroatoms, the values ​​of the molecular weight α and the ratio α / β can be controlled to the numerical range described above by converting the molecular structure through a chemical reaction.

[0065] ((A) Epoxy resin)

[0066] The epoxy resin composition of the present embodiment contains (A) an epoxy resin.

[0067] (A) As for the epoxy resin, examples include, but are not limited to: 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, tetrabromo bisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, tetrabromo biphenyl 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, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcinol type epoxy resin, methyl resorcinol type epoxy resin, catechol type epoxy resin, N,N-diglycidylaniline type epoxy resin, ethylene oxide Difunctional epoxy resins such as addition-type bisphenol A epoxy resin, propylene oxide addition-type bisphenol A epoxy resin, ethylene oxide addition-type bisphenol F epoxy resin, and propylene oxide addition-type bisphenol F epoxy resin; trifunctional epoxy resins such as trisphenol-type epoxy resin, N,N-diglycidylaminobenzene-type epoxy resin, o-(N,N-diglycidylamino)toluene-type epoxy resin, triazine-type epoxy resin, ethylene oxide addition-type trisphenol-type epoxy resin, and propylene oxide addition-type trisphenol-type epoxy resin; tetrafunctional epoxy resins such as tetraglycidyl diaminodiphenylmethane-type epoxy resin and diaminobenzene-type epoxy resin; Examples include polyfunctional epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl ethane type epoxy resin, dicyclopentadiene type epoxy resin, naphtholaralkyl type epoxy resin, and bromolated phenol novolak type epoxy resin; and alicyclic epoxy resins.

[0068] These may be used as a single type or in combination with two or more types.

[0069] In addition, epoxy resins modified from isocyanates, etc., can also be used in combination.

[0070] The epoxy resin described above is not particularly limited, but, for example, a bisphenol F type epoxy resin alone, a combination of a bisphenol F type epoxy resin and a bisphenol A type epoxy resin, or a combination of a bisphenol F type epoxy resin and a naphthalene type epoxy resin can be suitably used.

[0071] In the epoxy resin composition of the present embodiment, (A) the content of the epoxy resin is not particularly limited, but with respect to the liquid component of the epoxy resin composition, it is preferably 60 mass% or more and 95 mass% or less, more preferably 65 mass% or more and 90 mass% or less, and even more preferably 70 mass% or more and 85 mass% or less.

[0072] (A) By setting the epoxy resin content to the range described above, high adhesion tends to be obtained.

[0073] ((B) Curing agent containing heteroatoms)

[0074] The epoxy resin composition of the present embodiment comprises (B) a curing agent having heteroatoms.

[0075] (B) A curing agent having heteroatoms is a curing agent that satisfies the conditions of molecular weight α and ratio α / β described above.

[0076] (B) The curing agent having heteroatoms is not particularly limited as long as it has heteroatoms, but it is preferable that it is a curing agent having heteroatoms in the main chain. In addition, the curing agent having heteroatoms in the main chain is not particularly limited, but from the viewpoint of functioning as a latent curing agent, a curing agent having nitrogen atoms and oxygen atoms in the main chain is preferred, and a curing agent having NN bonds in the main chain is more preferable. (B) As a curing agent having heteroatoms, for example, the following amineimide compounds may be suitably used from the viewpoint of functioning as a latent curing agent.

[0077] (B) The curing agent having heteroatoms is preferably an amineimide compound represented by the following formulas (1), (2) or (3) in order to ensure that the epoxy resin composition of the present embodiment has excellent penetration, excellent curing properties, and storage stability (hereinafter referred to as “amineimide compound in the present embodiment”).

[0078]

[0079] In formulas (1) to (3), R1 each independently represents a monovalent or n-valent organic group having 1 to 15 carbon atoms, which may have a hydrogen atom, or a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 each independently represent an alkyl group, an aryl group, an aralkyl group having 1 to 12 carbon atoms, or a heterocyclic group having 7 or fewer carbon atoms connected by R2 and R3, which may have an unsubstituted or substituent group; R4 each independently represents a monovalent or n-valent organic group having 1 to 30 carbon atoms, which may include a hydrogen atom or an oxygen atom; and n represents an integer from 1 to 3.

[0080] In the present embodiment, the amineimide compound is preferably a liquid compound at room temperature. In the present embodiment, the viscosity at 25°C may be used as an indicator of being "liquid at room temperature." Furthermore, from the view that solubility, dispersibility, and penetration into a substrate are further improved in the epoxy resin composition of the present embodiment, the viscosity of the amineimide compound at 25°C in the present embodiment 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. Additionally, the lower limit of the viscosity at 25°C is not particularly limited, but it is preferably 0.01 Pa·s or more. The viscosity of the amineimide compound in the present embodiment can be controlled, for example, by adjusting the functional groups R1 to R4 in Formulas (1) to (3). In addition, the viscosity (Pa·s) of the amineimide compound at 25°C in the present embodiment can be measured, for example, by dropping a amineimide compound (about 0.3 mL) into a measuring cup and measuring it with an E-type viscometer (Tokki Sangyo Co., Ltd. “TVE-35H”) after 15 minutes have passed since the sample temperature reached 25°C.

[0081] In the above formulas (2) and (3), n represents an integer from 1 to 3. From the perspective of the adhesion of the epoxy resin composition of the present embodiment, n in formulas (2) and (3) is preferably 2 or 3.

[0082] In the above formulas (1), (2) and (3), R1 each independently represents a hydrogen atom or a “monolithic or n-valent organic group having 1 to 15 carbon atoms, which may have a hydroxyl group, a carbonyl group, or an ester bond.” Examples of such organic groups are not particularly limited, but include a “hydrocarbon group,” a “group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted by a hydroxyl group or a carbonyl group,” or a “group in which a part of the carbon atom constituting the hydrocarbon group is substituted by an ester bond or an ether bond.”

[0083] Examples of the above hydrocarbon groups include straight-chain, 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, pentinyl, hexinyl, octinyl, decinyl, dodecinyl, hexadecinyl, and octadecinyl groups; aryl groups such as phenyl groups; and aralkyl groups comprising combinations of alkyl groups such as methylphenyl, ethylphenyl, and propylphenyl groups with phenyl groups.

[0084] In addition, the organic group represented by R1 in the above formulas (1) to (3) may be unsubstituted or may have a substituent. Examples of substituents include, but are not limited to, halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azyl groups, thiol groups, sulfo groups, nitro groups, hydroxyl groups, acyl groups, and aldehyde groups.

[0085] The number of carbon atoms of the organic group represented by R1 in the above formulas (1) to (3) is 1 to 15, preferably 1 to 12, and more preferably 1 to 7. As the number of carbon atoms of the organic group represented by R1 is within the above-described range, the curing performance of the amineimide compounds of the above formulas (1) to (3) tends to be further improved. In addition, as the number of carbon atoms of the organic group represented by R1 is within the above-described range, the ease of obtaining raw materials for preparing the above formulas (1) to (3) is further improved.

[0086] Among the above, it is preferable that the organic group represented by R1 in formula (1) or (3) be the group represented by the following formula (4) or (5). By having the group represented by the following formula (4) or (5) as R1 in formula (1) or (3), the curing performance of the amineimide compound tends to be further improved.

[0087]

[0088] Among the above equations (4) and (5), R 11 Each represents, independently, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms, and n represents, independently, an integer from 0 to 6.

[0089] Among the above, a group in which n in Formula (5) is 0 or 1 is preferred. Accordingly, the amineimide compound represented by Formula (1) or (3) has a diketone structure in the R1-C(=O)- structure. Such a diketone structure tends to further improve the curing performance of the amineimide compound.

[0090] Also, R in the above equation (4) or (5) 11 The number of carbon atoms and n are adjusted so that the maximum value of the number of carbon atoms of the group represented by the above equation (4) or (5) does not exceed 15. In addition, R 11Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, the aryl group, or the aralkyl group having 7 to 9 carbon atoms include those similar to the organic group represented by R1 described above.

[0091] In addition, it is preferable that the organic group represented by R1 in the above formula (2) be a group represented by the following formula (6) or (7). By having the above formula (2) have a group represented by the following formula (6) or (7) as R1, it is easier to obtain a liquid amineimide compound at room temperature, and the curing performance of the amineimide compound tends to be further improved.

[0092]

[0093] Among the above equations (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.

[0094] Among the above, R in the above equation (7) 13 A single bond or a methyl group is preferred. Accordingly, the amineimide compound represented by Formula (2) has a diketone structure within the R1-C(=O)- structure. This diketone structure tends to further improve the curing performance of the amineimide compound. In addition, R 12 and R 13 Examples of the alkyl group, aryl group, or aralkyl group having 1 to 5 carbon atoms, in this case, include those similar to the organic group represented by R1 described above.

[0095] In the above formulas (1), (2) and (3), R2 and R3 each independently represent an alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, having an unsubstituted or substituent group, or a heterocyclic group having 7 or fewer carbon atoms connected by R2 and R3.

[0096] As for the alkyl group having 1 to 12 carbon atoms represented by R2 or R3, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl groups, but are not limited to the following; branched alkyl groups such as isopropyl, isobutyl, t-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl groups.

[0097] In addition, the above-described alkyl group may be a combination of a straight-chain alkyl group or a branched alkyl group and a cyclic alkyl group. In addition, the above-described alkyl group may include an unsaturated linkage group.

[0098] The number of carbon atoms in the alkyl group represented by R2 or R3 is, independently, 1 to 12, preferably 2 to 10, and more preferably 5 to 10. From the perspective of handling, it is preferable to have 2 or more carbon atoms in the alkyl group represented by R2 or R3. In addition, by making the number of carbon atoms in the alkyl group represented by R2 or R3 5 or more, it is easy to obtain a liquid amineimide compound at room temperature, and the curing performance of the amineimide compound tends to be further improved.

[0099] In addition, aryl groups represented by R2 or R3 are not limited to the following, but examples include phenyl groups and naphthyl groups.

[0100] In addition, the aralkyl group represented by R2 or R3 is not limited to the following, but examples include a methylphenyl group, an ethylphenyl group, a methyl naphthyl group, and a dimethyl naphthyl group. Among 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. As a result, the curing performance of the amineimide compound tends to be further improved.

[0101] In addition, 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 or more and 20 or less.

[0102] Substituents of alkyl, aryl, or aralkyl groups represented by R2 or R3 include, but are not limited to, halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azimo groups, thiol groups, sulfo groups, nitro groups, hydroxyl groups, acyl groups, and aldehyde groups.

[0103] R2 and R3 may be connected to form a heterocyclic ring with 7 or fewer carbon atoms. Such a heterocyclic ring is not limited to the following, but for example, R, represented by the following formula (8). 23 N of formulas (1), (2) or (3) + Examples include heterocyclic rings formed by . Also, R 23 represents the device connected by R2 and R3.

[0104]

[0105] In Equation (8), R 23 is N + Along with, it represents a group that forms a heterocyclic structure.

[0106] R 23 and N + Examples of heterocyclic rings formed by [the band] include, but are not limited to the following: 4-membered rings such as the azetidine ring; 5-membered rings such as the pyrrolidine ring, pyrrole ring, morpholine ring, and thiazine ring; 6-membered rings such as the piperidine ring; and 7-membered rings such as the hexamethyleneimine ring and azepine ring.

[0107] Among these, as heterocyclic rings, pyrrole rings, morpholine rings, thiazine rings, piperidine rings, hexamethyleneimine rings, and azepine rings are preferred, and six-membered and seven-membered rings are more preferred. By having these groups, liquid amineimide compounds are easily obtained at room temperature, and the curing performance of the amineimide compounds tends to be further improved.

[0108] In addition, the substituents having a heterocyclic ring having 7 or fewer carbon atoms are not limited to the following, but may include, for example, alkyl groups, aryl groups, or the substituents in R2 and R3 described above. In addition, when the heterocyclic ring has an alkyl group as a substituent, N + Examples include methyl groups bonded to adjacent carbon atoms.

[0109] In the above formulas (1), (2) and (3), R4 each independently represents a hydrogen atom or an "organic group having 1 to 30 carbon atoms, which may include an oxygen atom, and having a monovalent or n-valent value." Examples of such organic groups are not limited to the following, but include, for instance, a "hydrocarbon group," a "group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted by a hydroxyl group, a carbonyl group, or a group containing a silicon atom," or a "group in which a portion of the carbon atoms constituting the hydrocarbon group are substituted by an ester bond, an ether bond, or a silicon atom."

[0110] As a hydrocarbon group represented by R4, examples include, but are not limited to, straight-chain, 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, pentinyl, hexinyl, octinyl, decinyl, dodecinyl, hexadecinyl, and octadecinyl groups; aryl groups such as phenyl groups; or aralkyl groups comprising a combination of alkyl groups such as methylphenyl, ethylphenyl, and propylphenyl groups and phenyl groups.

[0111] In addition, the hydrocarbon group represented by R4 includes bisphenol backbones such as bisphenol A backbone, bisphenol AP backbone, bisphenol B backbone, bisphenol C backbone, bisphenol E backbone, and bisphenol F backbone. Organic groups containing bisphenol backbones are not limited to the following, but include, for example, groups in which a polyoxyalkylene group is added to the hydroxyl group of each bisphenol backbone.

[0112] Among these, the organic group represented by R4 in the above 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. In addition, these preferred groups may have substituents. By having such groups, the curing performance of the amineimide compound tends to be further improved. In addition, the glass transition temperature (Tg) of the cured product obtained using the amineimide compound tends to be further improved.

[0113] 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. As the number of carbon atoms in the organic group represented by R4 is within the above-described range, the curing performance of the amineimide compound tends to be further improved. In addition, the Tg of the cured product obtained using the amineimide compound is further improved, and as the number of carbon atoms in the organic group represented by R4 is within the above-described range, the ease of obtaining raw materials for preparing the amineimide compound is further improved.

[0114] Among the above, R4 in formula (1) or (2) is preferably a straight-chain or branched alkyl group having 3 to 12 carbon atoms, or a straight-chain or branched alkenyl group having 3 to 6 carbon atoms. By having such a group, the curing performance of the amineimide compound tends to be further improved.

[0115] In addition, it is preferable that R4 in the above formula (3) be a group represented by the following formula (9) or (10). By having a group represented by the following formula (9) or (10) as R4 in the above formula (3), the curing performance of the amineimide compound tends to be further improved.

[0116]

[0117] Among equations (9) and (10), R 41 and R 42 Each independently represents an alkyl group, an aryl group, or an aralkyl group having 1 to 5 carbon atoms, and each independently represents an integer from 0 to 10.

[0118] The epoxy resin composition of the present embodiment may include a plurality of amineimide compounds represented by formulas (1), (2), or (3) as a curing agent. By including a plurality of amineimide compounds, it is possible to control the curing temperature and viscosity, and an improvement in properties is obtained. In addition, the epoxy resin composition of the present embodiment may include a plurality of amineimide compounds with different structures among the amineimide compounds represented by formulas (1) to (3), which are compounds represented by the same formula.

[0119] (B) When using an amineimide composition containing multiple amineimide compounds as a curing agent having heteroatoms, the amineimide composition may be obtained by mixing multiple amineimide compounds, or by simultaneously producing multiple amineimide compounds in the method for producing amineimide compounds described below.

[0120] Method for preparing amineimide compounds and amineimide compositions

[0121] The method for preparing the amineimide compound having heteroatoms as a curing agent (B) used in the epoxy resin composition of the present embodiment is not particularly limited, provided that the method obtains an amineimide compound having the structure of any of the formulas (1) to (3) described above. The method for preparing the amineimide composition may include a method of mixing a plurality of amineimide compounds obtained by the method described below, or a method of simultaneously preparing a plurality of amine compounds to obtain a mixture.

[0122] As an example of a method for preparing an amineimide compound, a method having a reaction process in which an ester compound (BA), a hydrazine compound (BB), and a glycidyl ether compound (BC) are reacted can be cited. A method for preparing an amineimide compound will be described below. In addition, in the following, each compound (BA) to (BC) may be referred to as "component (BA), etc."

[0123] Examples of ester compounds (BA) include, but are not limited to, monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, and cyclic esters.

[0124] Examples of monocarboxylic acid ester compounds include, but are not limited to the following: methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, isovalermethyl, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonicate, methyl isocrotonicate, methyl benzoyl formate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl, etc. In addition, ethyl esters, propyl esters, etc. may be used instead of these.

[0125] Examples of dicarboxylic acid ester compounds include, but are not limited to the following: dimethyl oxalate, dimethyl malonicate, dimethyl succinate, dimethyl tartarate, dimethyl glutarate, dimethyl adipoyl adipose, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetone dicarboxylate, and diethyl 1,3-acetone dicarboxylate. Additionally, cyclic esters, etc., may be used instead of these.

[0126] Examples of cyclic esters include, but are not limited to, α-acetactone, β-propion lactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, etc. In addition, diethyl esters, dipropyl esters, etc. may be used instead of these.

[0127] Among these, (B) with respect to the curability and liquefaction of amineimide compounds as curing agents, the ester compound (BA) is ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, isovalermethyl, methyl pivalate, methyl acrylate, methyl methacrylate, methyl crotonicate, methyl isocrotonicate, methyl benzoyl formate, dimethyl oxalate, dimethyl malonicate, dimethyl succinate, dimethyl tartarate, dimethyl glutarate, dimethyl adipicate, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetone dicarboxylate, and diethyl 1,3-acetone dicarboxylate, γ-butyrolactone, δ-valerolactone, and γ-valerolactone are preferred.

[0128] In addition, among these, from the perspective of availability, ethyl lactate, ethyl propionate, methyl mandelate, methyl benzoyl formate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipoyl adipose, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and 1,3-diethyl acetone dicarboxylate are more preferred as ester compounds (BA).

[0129] The ester compound (BA) may be used alone or in combination with two or more types.

[0130] Hydrazine compounds (BB) are not limited to the following, but include, for example, 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-aminohomopipiridine, 1-amino-2,6-dimethylpiperidine, 1-aminopyrrolidine, 1-amino-2-methylpyrrolidine, Examples include 1-amino-2-phenylpyrrolidine and 1-aminomorpholine.

[0131] Among these, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred as hydrazine compounds (BB) in terms of curability and liquefaction. Furthermore, among these, dibenzylhydrazine and 1-aminopiperidine are more preferred in terms of availability and safety.

[0132] Hydrazine compounds (BB) may be used alone or in combination of two or more.

[0133] As for the glycidyl ether compound (BC), examples may be used, although not limited to the following: monofunctional monoglycidyl ether compounds or polyglycidyl ether compounds with two or more functions.

[0134] Examples of monoglycidyl ether compounds include, but are not limited to the following: methylglycidyl ether, ethylglycidyl ether, n-butylglycidyl ether, t-butylglycidyl ether, 2-ethylhexylglycidyl ether, dodecylglycidyl ether, higher alcohol glycidyl ether, allylglycidyl ether, phenylglycidyl ether, cresylglycidyl ether, orthophenylphenolglycidyl ether, benzylglycidyl ether, biphenylglycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilylglycidyl ether, 3-[diethoxy(methyl)silyl]propyl glycidyl ether, etc.

[0135] Polyglycidyl ether compounds are not limited to the following, but include, for example, aliphatic polyglycidyl ethers such as 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, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol polyglycidyl ether, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, and ethylene oxide addition type bisphenol A type Examples include diglycidyl ethers, propylene oxide addition type bisphenol A type diglycidyl ethers, and hydrides of their condensates, as well as alicyclic polyglycidyl ether compounds, aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ethers.

[0136] Among these, (B) in terms of the curability and liquefaction of the amineimide compound as a curing agent, the glycidyl ether compound (BC) is preferably methylglycidyl ether, ethylglycidyl ether, n-butylglycidyl ether, t-butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, phenylglycidyl ether, t-butyldimethylsilylglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, ethylene oxide-added bisphenol A type diglycidyl ether, or propylene oxide-added bisphenol A type diglycidyl ether.

[0137] In addition, among these, from the perspective of availability and the Tg of the cured product, n-butylglycidyl ether, t-butylglycidyl ether, 2-ethylhexylglycidyl ether, allylglycidyl ether, trimethylolpropane polyglycidyl ether, ethylene oxide addition type bisphenol A type diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, and propylene oxide addition type bisphenol A type diglycidyl ether are more preferred as glycidyl ether compounds (BC).

[0138] Glycidyl ether compounds (BC) may be used alone or in combination of two or more.

[0139] The amounts of ester compound (BA), hydrazine compound (BB), and glycidyl ether compound (BC) added to the reaction system for preparing an amineimide compound can be set based on the molar ratio of functional groups. The ester group of ester compound (BA) is preferably 0.8 to 3.0 moles, more preferably 0.9 to 2.8 moles, and even more preferably 0.95 to 2.5 moles per 1 mole of primary amine of hydrazine compound (BB). Additionally, the glycidyl group of glycidyl ether compound (BC) is preferably 0.8 to 2.0 moles, more preferably 0.9 to 1.5 moles, and even more preferably 0.95 to 1.4 moles per 1 mole of primary amine of hydrazine compound (BB).

[0140] By controlling the amount of glycidyl groups of the glycidyl ether compound (BC) added to 1 mole of the primary amine of the hydrazine compound (BB), an amineimide composition comprising an amineimide compound represented by formulas (1) and (3) can be simultaneously prepared. Specifically, the glycidyl groups of the glycidyl ether compound (BC) are 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 with respect to 1 mole of the primary amine of the hydrazine compound (BB).

[0141] In the method for preparing the amineimide compound and amineimide composition described above, a solvent may be used in order to proceed with the reaction uniformly.

[0142] The solvent is not particularly limited as long as it does not react with the above (BA) to (BC) components, but examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, t-butyl alcohol; ethers such as tetrahydrofuran and diethyl ether.

[0143] The reaction temperature of the above (BA) to (BC) components is preferably 10 to 100°C, and more preferably 40 to 90°C. When the reaction temperature is 10°C or higher, the reaction proceeds faster, and the purity of the obtained amineimide compound tends to be further improved. In addition, when the reaction temperature is 90°C or lower, the polymerization reaction between the glycidyl ether compounds (BC) can be efficiently suppressed, so the purity of the amineimide compound tends to be further improved.

[0144] The reaction time of the above (BA) to (BC) components is preferably 1 hour or more and 168 hours or less, more preferably 1 hour or more and 96 hours or more, and even more preferably 1 hour or more and 48 hours or less.

[0145] After the reaction is finished, the obtained reaction product can be purified by known purification methods such as washing, extraction, recrystallization, and column chromatography. For example, after washing the reaction solution dissolved in an organic solvent with water, the unreacted raw material or organic solvent can be removed from the reaction solution and the amineimide compound can be recovered by heating the organic layer under atmospheric pressure or reduced pressure. In addition, the amineimide compound can be recovered by purification using column chromatography.

[0146] The solvent used for the cleaning described above is not particularly limited as long as it can dissolve the residue of the raw material, but 1-hexane, 1-pentane, and cyclohexane are preferred from the perspective of yield, purity, and ease of removal.

[0147] The organic solvent used for the extraction described above is not particularly limited as long as it can dissolve the target amineimide compound, but ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred from the perspective of yield, purity, and ease of removal, and it is more preferable to use ethyl acetate, chloroform, toluene, and methyl isobutyl ketone.

[0148] The packing material used in column chromatography may be a known material such as alumina or silica gel, and the developing solvent may be a known material such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, etc., used alone or in combination.

[0149] <Curing agent having heteroatoms other than amineimide compounds (B)>

[0150] The epoxy resin composition of the present embodiment may use (B) a curing agent having heteroatoms, provided that the molecular weight of the curing agent and the number of heteroatoms in its structure are within a specific range, a curing agent having heteroatoms other than the amineimide compound described above. Examples of such curing agents having heteroatoms include, but are not limited to the following: amine-based curing agents such as imidazoles, aliphatic amines, aromatic amines, and polyamide resins; amide-based curing agents; acid anhydride-based curing agents such as acid anhydrides; phenol-based curing agents such as phenols, polyhydric phenol compounds and modified products thereof; BF3-amine complexes; guanidine derivatives, etc.

[0151] These curing agents may be used as a single type or in combination of two or more types.

[0152] <(B) Content of curing agent having heteroatoms>

[0153] In the epoxy resin composition of the present embodiment, the total content of (B) a curing agent having heteroatoms is preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of (A) epoxy resin.

[0154] (B) By setting the total content of the curing agent having heteroatoms to the range described above, the curing reaction of the epoxy resin composition of the present embodiment is sufficiently promoted, and there is a tendency to obtain even better cured properties.

[0155] In addition, in the epoxy resin composition of the present embodiment, when the amineimide compound described above is used as a curing agent, the total content of the amineimide compound is, as described above, preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, with respect to 100 parts by mass of the total amount of (A) epoxy resin. By setting the total content of the amineimide compound in the present embodiment to the range described above, the curing reaction of the epoxy resin composition is sufficiently promoted, and there is a tendency to obtain even better cured properties.

[0156] In addition, when the amineimide compound in the present embodiment is used as a curing accelerator for a curing agent (B) having heteroatoms other than the amineimide compound, the total content of the amineimide compound in the present embodiment 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, with respect to 100 parts by mass of the total amount of (A) epoxy resin. By setting the content of the amineimide compound in the present embodiment to the above-described range, it functions as a curing catalyst for the curing agent (B) having heteroatoms other than the amineimide compound in the present embodiment, and the curing reaction is sufficiently promoted, and there is a tendency to obtain even better cured product properties.

[0157] In the epoxy resin composition of the present embodiment, (B) a curing agent having heteroatoms and other curing agents other than (B) may be used in combination. In this case, the curing agent having (B) heteroatoms may function as a curing accelerator for other curing agents. When the curing agent having (B) heteroatoms and other curing agents are used in combination, the total content of the curing agent having (B) heteroatoms is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 15 parts by mass or less, with respect to 100 parts by mass of the total amount of (A) epoxy resin. When used in combination with other curing agents, by setting the content of the curing agent having (B) heteroatoms to the range described above, it functions as a curing catalyst for other curing agents, sufficiently promotes the curing reaction, and tends to obtain even better cured product properties.

[0158] (B) Other curing agents other than the curing agent of (B) that can be used in combination with a curing agent having heteroatoms may include, but are not limited to the following, amine-based curing agents such as imidazoles, aliphatic amines, aromatic amines, and polyamide resins that do not satisfy the molecular weight α and ratio α / β described above; amide-based curing agents; acid anhydride-based curing agents such as acid anhydrides; phenol-based curing agents such as phenols, polyhydric phenol compounds and modified products thereof, BF3-amine complexes, guanidine derivatives, etc.

[0159] These other curing agents may be used as a single type or in combination of two or more types.

[0160] In addition, in the epoxy resin composition of the present embodiment, the total content of the curing agent having (B) heteroatoms in the epoxy resin composition is preferably 0.4 mass% to 50 mass% from the perspective of compatibility of reactivity and stability. From the perspective of reactivity, it is more preferably 2.0 mass% or more, even more preferably 8.1 mass% or more, and even more preferably 9.0 mass% or more. In addition, from the perspective of storage stability, it is more preferably 40 mass% or less, even more preferably 25 mass% or less, and even more preferably 22 mass% or less.

[0161] ((C) Weapon Filler)

[0162] The epoxy resin composition of the present embodiment may contain an inorganic filler as needed. By using an inorganic filler, the low thermal linear expansion of the resulting cured product can be increased. As for the inorganic filler, it is not particularly limited, but examples include fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride, etc.

[0163] In the epoxy resin composition of the present embodiment, the content of (C) an inorganic filler is preferably greater than 5 mass% and less than or equal to 98 mass% with respect to the entire epoxy resin composition of the present embodiment, more preferably greater than or equal to 10 mass% and less than or equal to 95 mass%, even more preferably greater than or equal to 10 mass% and less than or equal to 90 mass%, and even more preferably greater than or equal to 10 mass% and less than or equal to 87 mass%. By setting the content of (C) an inorganic filler to the above-described range, a cured product with low thermal linear expansion tends to be obtained.

[0164] ((D) Stabilizer)

[0165] The epoxy resin composition of the present embodiment may include (D) a stabilizer as needed. (D) As a stabilizer, examples include monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, or cyclic lactone compounds, although not limited to the following.

[0166] As the above stabilizer, for example, a compound represented by the following formula (A) or (B) may be used.

[0167]

[0168] In formula (A), R5 and R6 each independently represent a monovalent or n-valent organic group having 1 to 15 carbon atoms, which may have a hydrogen atom, or a hydroxyl group, a carbonyl group, an ester bond, or an ether bond, and n represents an integer from 2 to 3.

[0169]

[0170] In formula (B), R7 represents 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, and n represents an integer from 2 to 3.

[0171] In the above formula (A), R5 and R6 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, or an ester bond.

[0172] In addition, in the above formula (B), R7 represents a “monolithic 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.”

[0173] These organic groups are not limited to the following, but include, for example, a “hydrocarbon group” similar to R1 in the above-described formula (1), a “group in which a hydrogen atom bonded to a carbon atom in the hydrocarbon group is substituted by a hydroxyl group or a carbonyl group,” or a “group in which a part of the carbon atom constituting the hydrocarbon group is substituted by an ester bond or an ether bond.”

[0174] As the monocarboxylic acid ester compound used as the (D) stabilizer, examples include, but are not limited to, methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, isovalermethyl, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonicate, methyl isocrotonicate, methyl benzoyl formate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl, etc. In addition, ethyl esters, propyl esters, etc. may be used instead of these.

[0175] As the above (D) stabilizer, the above dicarboxylic acid ester compound is not limited to the following, but examples include dimethyl oxalate, dimethyl malonicate, dimethyl succinate, dimethyl tartarate, dimethyl glutarate, dimethyl adipoyl adipose, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetone dicarboxylate, and diethyl 1,3-acetone dicarboxylate.

[0176] As the above-mentioned cyclic ester compound used as the (D) stabilizer, examples include α-acetactone, β-propion lactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, etc., although not limited to the following. In addition, diethyl esters, dipropyl esters, etc. may be used instead of these.

[0177] The epoxy resin composition of the present embodiment may use other stabilizers in addition to the stabilizers described above. Other stabilizers may include, but are not limited to, Lewis acid compounds containing boron, aluminum, gallium, indium, etc., or acidic compounds such as carboxylic acids, phenols, and organic acids.

[0178] In the epoxy resin composition of the present embodiment, the content of (D) the stabilizer is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, and even more preferably 1 part by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of (A) epoxy resin. By setting the content of (D) the stabilizer to the above-described range, an epoxy resin composition with excellent storage stability tends to be obtained.

[0179] (Other formulations)

[0180] The epoxy resin composition of the present embodiment may further contain other compounding agents, such as curing accelerators, flame retardants, silane coupling agents, release agents, and pigments, as needed. Suitable agents may be selected as long as they are within the range where the effects of the present embodiment are obtained. Examples of flame retardants include, but are not limited to the following: halides, phosphorus-containing compounds, nitrogen-containing compounds, inorganic flame retardant compounds, etc.

[0181] [Preparation and Cured Product of Epoxy Resin Composition]

[0182] The cured product of the present embodiment is a cured product obtained by curing the epoxy resin composition of the present embodiment described above.

[0183] The cured product of the present embodiment is obtained by heat-curing the epoxy resin composition described above, for example, by a conventionally known method. For example, the cured product of the present embodiment can be obtained by the following method.

[0184] First, the above-described (A) epoxy resin, (B) a curing agent having heteroatoms, and, if necessary, (C) an inorganic filler, (D) a stabilizer, a curing accelerator, and / or a compounding agent are sufficiently mixed using an extruder, a kneader, a roll, etc. until homogeneous to obtain an epoxy resin composition. Then, the epoxy resin composition is molded using a mold, a transfer molding machine, a compression molding machine, an injection molding machine, etc., and further heated at a temperature of about 80 to 200°C for about 2 to 10 hours to obtain a cured product of the present embodiment.

[0185] In addition, a cured product of the present embodiment can be obtained by, for example, the following method.

[0186] First, the above-described epoxy resin composition 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. Subsequently, a cured product may be obtained by heat-press molding the obtained prepreg.

[0187] 〔use〕

[0188] The epoxy resin composition of the present embodiment and the cured product obtained therefrom can be used for various applications where epoxy resin is used as a material. In particular, it is particularly useful for applications such as sealants (sealings formed from the cured product of the present embodiment), semiconductor sealants, adhesives (adhesives containing the epoxy resin composition of the present embodiment), printed circuit board materials, paints, and composite materials. Among these, it is suitable for use in semiconductor sealants such as underfills or moldings, conductive adhesives such as anisotropic conductive films (ACF), printed circuit boards such as solder resists or coverlay films, and composite materials such as prepregs formed by impregnating glass fibers or carbon fibers.

[0189] (Electronic absence)

[0190] The cured product of the above-described embodiment can be used to form an electronic component. Examples of the electronic component include, but are not limited to, semiconductor sealing materials such as underfill or molding, conductive adhesives such as ACF, printed circuit boards such as solder resist or coverlay film, and composite materials such as prepreg formed by impregnating glass fiber or carbon fiber.

[0191] Examples

[0192] Next, the present invention will be explained in more detail by means of synthetic examples, examples, and comparative examples, but the present invention is not limited by these.

[0193] Additionally, "parts" and "%" below are based on mass unless otherwise specified.

[0194] [(B) Synthesis of a curing agent having heteroatoms]

[0195] (B) An amineimide compound having heteroatoms was synthesized as a curing agent. Then, the molecular weight (molecular weight α) of the amineimide compound and the number of heteroatoms β of the amineimide compound were measured by ESI-MS, and it was confirmed that the target amineimide compound could be synthesized.

[0196] [Synthesized Example 1]

[0197] 7.08 g (0.060 mol) of ethyl lactate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 7.19 g (0.030 mol) of 1,6-hexanediol diglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove by-product alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 15.85 g (yield 92.2%) of a pale yellow liquid compound A (Compound A below): was obtained. The ESI-MS measurement was 575.36 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0198]

[0199] [Synthesized Example 2]

[0200] 6.12 g (0.060 mol) of ethyl propionate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 7.19 g (0.030 mol) of 1,6-hexanediol diglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove by-product alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 14.03 g (yield 86.4%) of pale yellow liquid compound B (Compound B below) was obtained. The ESI-MS measurement was 543.42 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0201]

[0202] [Synthesized Example 3]

[0203] 5.16 g (0.060 mol) of γ-butyrolactone, 6.00 g (0.060 mol) of 1-aminopiperidine, and 7.19 g (0.030 mol) of 1,6-hexanediol diglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction mixture was concentrated under reduced pressure at 60°C to remove unreacted raw materials by distillation, thereby obtaining a liquid product. Reacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 15.57 g (yield 86.2%) of a pale yellow liquid compound C (compound C below): was obtained. The ESI-MS measurement was 603.43 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0204]

[0205] [Synthesized Example 4]

[0206] 6.00 g (0.060 mol) of γ-valerolactone, 6.00 g (0.060 mol) of 1-aminopiperidine, and 7.19 g (0.030 mol) of 1,6-hexanediol diglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction mixture was concentrated under reduced pressure at 60°C to remove unreacted raw materials by distillation, thereby obtaining a liquid product. Reacted raw material residues were removed from this product by repeatedly washing it with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow liquid compound D (Compound D below): 16.08 g (yield 85.1%) was obtained. The ESI-MS measurement was 631.46 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0207]

[0208] [Synthesized Example 5]

[0209] 7.08 g (0.060 mol) of ethyl lactate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 10.36 g (0.030 mol) of bisphenol A type epoxy resin (EXA850CRP, DIC Co., Ltd.) were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Reacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 18.64 g (yield 90.6%) of pale yellow compound E (compound E below): was obtained. The ESI-MS measurement was 685.44 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0210]

[0211] [Synthesized Example 6]

[0212] 7.08 g (0.060 mol) of ethyl lactate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 5.81 g (0.020 mol) of a trifunctional glycidyl amine compound (jER630, Mitsubishi Chemical Corporation) were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove by-product alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow compound F (compound F below): 14.18 g (yield 89.1%) was obtained. The ESI-MS measurement value was 794.45 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0213]

[0214] [Synthesized Example 7]

[0215] 9.83 g (0.060 mol) of methyl benzoyl formate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 11.16 g (0.060 mol) of 2-ethylhexylglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow liquid compound G (compound G below): 23.82 g (yield 94.9%) was obtained. The ESI-MS measurement was 419.31 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0216]

[0217] [Synthesized Example 8]

[0218] 6.12 g (0.060 mol) of ethyl propionate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 7.80 g (0.060 mol) of n-butylglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Reacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 14.94 g (yield 94.9%) of a pale yellow liquid compound H (compound H below) was obtained. The ESI-MS measurement was 287.27 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0219]

[0220] [Synthesized Example 9]

[0221] 8.75 g (0.060 mol) of dimethyl succinate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 7.19 g (0.030 mol) of 1,6-hexanediol diglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove by-product alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 17.62 g (yield 89.3%) of pale yellow liquid compound I (Compound I below) was obtained. The ESI-MS measurement was 659.36 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0222]

[0223] [Synthesized Example 10]

[0224] 6.96 g (0.060 mol) of ethyl isobutyrate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 31.57 g (0.030 mol) of poly(ethylene glycol)diglycidyl ether (n9) were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow liquid compound J (compound J below): 22.49 g (yield 89.5%) was obtained. The ESI-MS measurement was 839.57 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0225]

[0226] [Synthesized Example 11]

[0227] 6.12 g (0.060 mol) of ethyl propionate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 31.57 g (0.030 mol) of poly(ethylene glycol)diglycidyl ether (n9) were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove by-product alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow liquid compound K (compound K below): 24.29 g (yield 85.4%) was obtained. The ESI-MS measurement was 811.51 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0228]

[0229] [Synthesized Example 12]

[0230] 6.12 g (0.060 mol) of ethyl propionate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 18.33 g (0.030 mol) of poly(ethylene glycol)diglycidyl ether (n4) were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove by-product alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow liquid compound L (compound L below): 14.82 g (yield 83.7%) was obtained. The ESI-MS measurement was 591.38 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0231]

[0232] [Synthesized Example 13]

[0233] 6.96 g (0.060 mol) of ethyl isobutyrate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 18.69 g (0.030 mol) of BisF-type epoxy resin were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Reacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 17.00 g (yield 86.9%) of a pale yellow liquid compound M (compound M below): was obtained. The ESI-MS measurement was 653.43 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0234]

[0235] [Synthesized Example 14]

[0236] 6.12 g (0.060 mol) of ethyl propionate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 18.69 g (0.030 mol) of BisF-type epoxy resin were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 15.35 g (yield 82.0%) of a pale yellow liquid compound N (compound N below) was obtained. The ESI-MS measurement was 625.40 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0237]

[0238] [Synthesized Example 15]

[0239] 6.96 g (0.060 mol) of ethyl isobutyrate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 16.29 g (0.030 mol) of naphthalene-type epoxy resin were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, 15.90 g (yield 86.6%) of a pale yellow liquid compound O (compound O below) was obtained. The ESI-MS measurement was 613.43 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0240]

[0241] [Synthesized Example 16]

[0242] 6.12 g (0.060 mol) of ethyl propionate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 16.29 g (0.030 mol) of naphthalene-type epoxy resin were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Reacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow liquid compound P (compound P below): 15.38 g (yield 87.8%) was obtained. The ESI-MS measurement was 585.38 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0243]

[0244] [Synthesized Example 17]

[0245] 6.12 g (0.060 mol) of ethyl propionate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 9.82 g (0.030 mol) of cresylglycidyl ether were mixed. This solution was reacted at 80°C for 4 hours while stirring. The resulting reaction solution was concentrated under reduced pressure at 60°C to remove byproduct alcohol and unreacted raw materials through distillation, thereby obtaining a liquid product. Unreacted raw material residues were removed by repeatedly washing this product with hexane. By concentrating this organic layer under reduced pressure again at 60°C, a pale yellow liquid compound Q (compound Q below): 8.13 g (yield 84.8%) was obtained. The ESI-MS measurement was 321.42 (H + Because it was ), the description in the table corresponding to molecular weight α was adopted.

[0246]

[0247] Next, an epoxy resin composition containing the compounds of each synthesis example was prepared according to the examples described below. Then, various properties described below were measured for each of the obtained epoxy resin compositions.

[0248] [(1) Shear adhesive strength]

[0249] Test specimens were prepared in accordance with JIS K 6850 using the epoxy resin compositions of the examples and comparative examples described below. Additionally, as the substrate, a substrate (cold-rolled copper plate) with dimensions of 25 mm in width × 100 mm in length × 1.6 mm in thickness in accordance with JIS C 3141 was used. The uncured test specimen was placed in a small high-temperature chamber "ST-110B2" manufactured by ESPEC Co., Ltd., which is stable at a temperature of 150°C, and heated for 2 hours to obtain a test specimen for measuring shear adhesive strength. After 2 hours, the structure (test specimen for measuring shear adhesive strength) was removed from the small high-temperature chamber and left in a room temperature environment to cool down until it reached room temperature. After cooling to room temperature, the maximum load at which the adhesive surface of the test specimen fractures and the specimen separates was measured using a Shimadzu Seisakusho “AGX-5kNX” with a load cell of 5kN and a speed of 5mm / min, and the value obtained by dividing the maximum separated load by the adhesive area was defined as the shear adhesive strength. From the obtained shear adhesive strength, “adhesion” was evaluated based on the following criteria.

[0250] 〔standard〕

[0251] ◎: Shear adhesive strength A is 16.0 MPa <A였다.

[0252] ○: Shear adhesive strength A is 13.5 MPa <A≤16.0㎫였다.

[0253] △: Shear adhesive strength A is 10.0 MPa <A≤13.5㎫였다.

[0254] ×: The shear adhesive strength A was A≤10 MPa.

[0255] [(2) Storage Stability]

[0256] The epoxy resin composition obtained in the examples and comparative examples described below was stored at 25°C for 72 hours, and the viscosity before and after storage was measured using a BM-type viscometer (25°C).

[0257] The ratio of the viscosity of the epoxy resin composition after storage to the viscosity of the epoxy resin composition before storage (viscosity increase factor) (=viscosity after storage / viscosity before storage) was calculated, and "storage stability (storage stability at room temperature)" was evaluated based on the following criteria.

[0258] ◎: The viscosity increase ratio was less than 1.75 times.

[0259] ○: The viscosity increase ratio was 1.75 times or more and less than 3 times.

[0260] ×: The viscosity increase ratio was more than 3 times.

[0261] [(3) Thermal wire expansion]

[0262] The epoxy resin compositions obtained in the examples and comparative examples described below were placed in a small high-temperature chamber "ST-110B2" manufactured by ESPEC Co., Ltd., which has a stable internal temperature of 150°C, and heated for 2 hours to obtain a cured product for TMA (thermomechanical analysis) measurement. After 2 hours, the structure was removed from the small high-temperature chamber and left in a room temperature environment to cool down to room temperature. After cooling to room temperature, TMA measurement was performed using a "Q400" manufactured by T.A. Instruments at a heating rate of 5°C / min. The value obtained by dividing the slope connecting two points at 30°C and 45°C by the length of the test specimen was defined as the "coefficient of thermal expansion." Thermal expansion properties were evaluated based on the following criteria.

[0263] ◎: The coefficient of thermal expansion was less than 50 ppm / ℃.

[0264] ○: The coefficient of thermal expansion was 50 ppm / ℃ or higher and less than 70 ppm / ℃.

[0265] △: The coefficient of thermal expansion was 70 ppm / ℃ or higher and less than 100 ppm / ℃.

[0266] ×: The coefficient of thermal expansion was 100 ppm / ℃ or higher, or could not be measured.

[0267] [Example 1]

[0268] 10g of epoxy resin (DIC Co., Ltd. “EXA-830CRP”) and 3.0g of compound A were placed in a plastic stirring container and mixed by stirring with a rotating / revolutionary mixer (Shinki Co., Ltd. “ARE-310”) to prepare an epoxy resin composition, and “adhesion” was evaluated by the shear adhesion evaluation method (1) described above, “storage stability at room temperature” was evaluated by the storage stability evaluation method (2) described above, and “thermal expansion” was evaluated by the thermal expansion evaluation method (3) described above.

[0269] [Example 2]

[0270] Except for changing compound A to compound B, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0271] [Example 3]

[0272] Except for changing Compound A to Compound C, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0273] [Example 4]

[0274] Except for changing Compound A to Compound D, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0275] [Example 5]

[0276] Except for changing Compound A to Compound E, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated. Storage stability could not be measured due to the high viscosity of the formulation, so it was indicated as "-" in the table below.

[0277] [Example 6]

[0278] Except for changing Compound A to Compound F, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated. Storage stability could not be measured due to the high viscosity of the formulation, so it was indicated as "-" in the table below.

[0279] [Example 7]

[0280] Except for changing compound A to compound G, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0281] [Example 8]

[0282] Except for changing compound A to compound H, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0283] [Example 9]

[0284] Except for changing Compound A to Compound I, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0285] [Example 10]

[0286] 10g of epoxy resin (DIC Co., Ltd. “EXA-830CRP”) and 0.7g of silica filler (Admatech “SO-E2”) were mixed using a 3-roller (AIMEX BR-150HCV), then placed in a plastic stirring container along with 3.0g of compound A, and mixed by stirring with a rotating / revolutionary mixer (Shinki Co., Ltd. “ARE-310”) to prepare an epoxy resin composition, and “adhesion” was evaluated by the shear adhesive strength evaluation method (1) described above, “storage stability at room temperature” was evaluated by the storage stability evaluation method (2) described above, and “thermal expansion” was evaluated by the thermal expansion evaluation method (3) described above.

[0287] [Example 11]

[0288] Except for the amount of silica filler added being 1.4g, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0289] [Example 12]

[0290] Except for the amount of silica filler added being 13.0 g, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0291] [Example 13]

[0292] Except for adding 0.7 g of ethyl propionate as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0293] [Example 14]

[0294] Except for adding 1.4 g of ethyl propionate as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0295] [Example 15]

[0296] Except for adding 0.7g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0297] [Example 16]

[0298] Except for adding 1.4 g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0299] [Example 17]

[0300] Except for adding 1.4 g of ethyl lactate as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0301] [Example 18]

[0302] Except for adding 1.4 g of dimethyl succinate as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0303] [Example 19]

[0304] Except for changing the amount of compound A added to 1.0 g, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0305] [Example 20]

[0306] Except for changing the epoxy resin used to 5.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Corporation) and 5.0 g of epoxy resin B ("jER630" manufactured by Mitsubishi Chemical Corporation), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0307] [Example 21]

[0308] Except for changing the epoxy resin used to 5.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Co., Ltd.) and 5.0 g of epoxy resin C ("HP4032D" manufactured by DIC Co., Ltd.), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0309] [Example 22]

[0310] Except for changing the epoxy resins used to 4.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Corporation), 4.0 g of epoxy resin B ("jER630" manufactured by Mitsubishi Chemical Corporation), 1.0 g of epoxy resin D ("jER1032H60" manufactured by Mitsubishi Chemical Corporation), and 1.0 g of epoxy resin F ("CDMDG" manufactured by Showa Denko Carens), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0311] [Example 23]

[0312] Except for changing the epoxy resins used to 4.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Co., Ltd.), 4.0 g of epoxy resin B ("jER630" manufactured by Mitsubishi Chemical Co., Ltd.), 1.0 g of epoxy resin D ("jER1032H60" manufactured by Mitsubishi Chemical Co., Ltd.), and 1.0 g of epoxy resin G ("YX8000" manufactured by Mitsubishi Chemical Co., Ltd.), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0313] [Example 24]

[0314] Except for changing the epoxy resins used to 4.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Co., Ltd.), 4.0 g of epoxy resin B ("jER630" manufactured by Mitsubishi Chemical Co., Ltd.), 1.0 g of epoxy resin D ("jER1032H60" manufactured by Mitsubishi Chemical Co., Ltd.), and 1.0 g of epoxy resin H ("YED216D" manufactured by Mitsubishi Chemical Co., Ltd.), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0315] [Example 25]

[0316] Except for changing the epoxy resins used to 4.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Corporation), 4.0 g of epoxy resin B ("jER630" manufactured by Mitsubishi Chemical Corporation), 1.0 g of epoxy resin E ("YX4000H" manufactured by Mitsubishi Chemical Corporation), and 1.0 g of epoxy resin I ("PETG" manufactured by Showa Denko Carens), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0317] [Example 26]

[0318] Except for changing the epoxy resins used to 4.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Co., Ltd.), 4.0 g of epoxy resin B ("jER630" manufactured by Mitsubishi Chemical Co., Ltd.), 1.0 g of epoxy resin E ("YX4000H" manufactured by Mitsubishi Chemical Co., Ltd.), and 1.0 g of epoxy resin J ("EX-321L" manufactured by Nagase Chemtex Co., Ltd.), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0319] [Example 27]

[0320] Except for changing compound A to compound J, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0321] [Example 28]

[0322] Except for changing compound A to compound K, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0323] [Example 29]

[0324] Except for changing Compound A to Compound K, changing the silica filler to "SE2200-SEJ" manufactured by Admatech, and increasing the amount of silica filler to 19.5 g, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0325] [Example 30]

[0326] Except for changing the silica filler to "SE205-SEJ" from Admatech, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0327] [Example 31]

[0328] Except for changing the silica filler to "SE203-SEJ" from Admatech, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0329] [Example 32]

[0330] Except for changing the silica filler to "SE1050-SET" from Admatech, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0331] [Example 33]

[0332] Except for the amount of silica filler added being 30.0 g, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0333] [Example 34]

[0334] Except for the amount of silica filler added being 39.0 g, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0335] [Example 35]

[0336] Except for using 31.0 g of "SE2200-SEJ" from Admatex and 46.0 g of "FB-5D" from Denka as silica fillers, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0337] [Example 36]

[0338] Except for using 36.0 g of "SE2200-SEJ" manufactured by Admatex and 57.0 g of "FB-5D" manufactured by Denka as silica fillers and adding 1.4 g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 24, and adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0339] [Example 37]

[0340] Except for changing the epoxy resin used to 6.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Co., Ltd.) and 4.0 g of epoxy resin H ("YED216D" manufactured by Mitsubishi Chemical Co., Ltd.), changing the silica filler used to 49.0 g of "SE2200-SEJ" manufactured by Admatex and 81.0 g of "FB-5D" manufactured by Denka, and adding 1.4 g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0341] [Example 38]

[0342] Except for changing the epoxy resin used to 0.6g of epoxy resin A ("EXA-830CRP" manufactured by DIC Co., Ltd.) and 0.4g of epoxy resin H ("YED216D" manufactured by Mitsubishi Chemical Co., Ltd.), changing the silica filler used to 27.4g of magnetic illusion of an NdFeB-based alloy with an average particle size of 100㎛, and adding 0.14g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0343] [Example 39]

[0344] Except for changing the epoxy resin used to 0.6g of epoxy resin A ("EXA-830CRP" manufactured by DIC Co., Ltd.) and 0.4g of epoxy resin H ("YED216D" manufactured by Mitsubishi Chemical Co., Ltd.), changing the silica filler used to 70.6g of magnetic illusion of an NdFeB-based alloy with an average particle size of 100㎛, and adding 0.14g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0345] [Example 40]

[0346] Except for changing compound A to compound L, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0347] [Example 41]

[0348] Except for changing compound A to compound M, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0349] [Example 42]

[0350] Except for changing compound A to compound N, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0351] [Example 43]

[0352] Except for changing compound A to compound O, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0353] [Example 44]

[0354] Except for changing compound A to compound P, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0355] [Example 45]

[0356] Except for changing compound A to compound Q, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0357] [Example 46]

[0358] Except for changing Compound A to 2.25g of Compound A and 0.75g of Compound E, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0359] [Example 47]

[0360] Except for changing Compound A to 2.0g of Compound B and 1.0g of Compound E, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0361] [Example 48]

[0362] Except for changing Compound A to Compound B 1.0g, Compound F 1.0g, and Compound N 1.0g, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0363] [Example 49]

[0364] Except for changing Compound A to 2.25g of Compound J and 0.75g of Compound M, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0365] [Example 50]

[0366] Except for changing Compound A to Compound J 2.0g and Compound Q 1.0g, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0367] [Example 51]

[0368] Except for changing Compound A to Compound K 2.25g and Compound N 0.75g, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0369] [Example 52]

[0370] Except for changing Compound A to 2.5g of Compound L and 0.5g of Compound N, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0371] [Example 53]

[0372] Except for changing Compound A to Compound L 2.0g and Compound Q 1.0g, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0373] [Example 54]

[0374] Except for changing Compound A to Compound K 2.25g and Compound P 0.75g, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0375] [Example 55]

[0376] Except for changing Compound A to Compound K 2.25g and Compound Q 0.75g, an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0377] [Example 56]

[0378] Except for changing Compound A to 0.975g of Compound A, 0.325g of Compound E, and 2.6g of Curing Agent A (4,4'-Diamino-3,3'-Diethyldiphenylmethane), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0379] [Example 57]

[0380] Except for compound A being 0.975g, compound E being 0.325g, curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane) being 2.6g, and the amount of silica filler being 13.0g, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0381] [Example 58]

[0382] Except for compound A being 0.975g compound J, 0.325g compound M, 2.6g curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane), and 13.0g silica filler, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0383] [Example 59]

[0384] Except for compound A being 0.975g compound K, 0.325g compound N, 2.6g curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane), and 13.0g silica filler, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesiveness, storage stability at room temperature, and thermal expansion properties were evaluated.

[0385] [Example 60]

[0386] Except for compound A being 0.693g, compound E being 0.231g, curing agent B (a liquid aromatic amine having a diaminodiphenylmethane backbone) being 1.8g, and the amount of silica filler being 13.0g, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0387] [Example 61]

[0388] Except for compound A being 0.693g compound J, 0.231g compound M, 1.8g curing agent B (a liquid aromatic amine having a diaminodiphenylmethane backbone), and 13.0g silica filler, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0389] [Example 62]

[0390] Except for compound A being 0.693g compound K, 0.231g compound N, 1.8g curing agent B (a liquid aromatic amine having a diaminodiphenylmethane backbone), and 13.0g silica filler, an epoxy resin composition was prepared in the same manner as in Example 10, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0391] [Comparative Example 1]

[0392] Except for changing compound A to 3.6 g of curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0393] [Comparative Example 2]

[0394] Except for changing compound A to 2.8 g of curing agent B (a liquid aromatic amine having a diaminodiphenylmethane backbone), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0395] [Comparative Example 3]

[0396] Except for changing compound A to 9.3 g of curing agent C ("HN5500" manufactured by Showa Denko Materials Co., Ltd.) and adding 0.05 g of 2E4MZ (2-ethyl-4-methylimidazole) as a curing accelerator, an epoxy resin composition was prepared in the same manner as in Example 1, and adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0397] Curing agent C is an acid anhydride, and its molecular weight α is 168.

[0398] [Comparative Example 4]

[0399] Except for changing compound A to 0.8 g of curing agent D (dicyandiamide (DICY)), an epoxy resin composition was prepared in the same manner as in Example 1, and the adhesion, storage stability at room temperature, and thermal expansion properties were evaluated.

[0400] The composition and evaluation results of each example and comparative example are shown in the table below.

[0401]

[0402]

[0403]

[0404]

[0405]

[0406]

[0407]

[0408]

[0409] From the results of each table, it was confirmed that the epoxy resin composition using a curing agent having a specific molecular weight (molecular weight α) and molecular structure (ratio α / β) has excellent adhesion.

[0410] In addition, from the results of each table, it was confirmed that an epoxy resin composition having a specific molecular weight and molecular structure, and using an amineimide compound in the present embodiment as a curing agent, exhibits good storage stability.

[0411] On the other hand, it was confirmed that storage stability or adhesion was reduced when a compound with a molecular weight or molecular structure outside the scope of the claims was used as a curing agent. Specifically, the liquid aromatic amine used in Comparative Examples 1 and 2 and the acid anhydride used in Comparative Example 3 each showed reduced adhesion, and it was also confirmed that storage stability was reduced in Comparative Examples 1 and 2.

[0412] In addition, from the results of Comparative Example 4, it can be seen that when the ratio α / β of the curing agent is less than 30, the adhesion and thermal expansion properties decrease.

[0413] From the results of Examples 10 and 11, it was confirmed that excellent low thermal linear expansion is exhibited by adding an inorganic filler.

[0414] In addition, from the results of Examples 12 to 17, it was confirmed that storage stability is further improved by adding a stabilizer having a specific structure.

[0415] This application is based on Japanese patent application (JP 2021-213746) filed with the Japan Patent Office on December 28, 2021, the contents of which are incorporated herein by reference. Industrial applicability

[0416] The epoxy resin composition of the present invention has industrial applicability as a sealant, adhesive, printed circuit board material, paint, composite material, semiconductor sealant such as underfill or molding, conductive adhesive such as ACF, printed circuit board such as solder resist or coverlay film, and composite material such as prepreg formed by impregnating glass fiber or carbon fiber.

Claims

Claim 1 (A) an epoxy resin and (B) a curing agent having heteroatoms, wherein the molecular weight α of the curing agent having heteroatoms (B) is 200 ≤ α ≤ 1200, the ratio α / β of the number of heteroatoms β in the structure of the curing agent having heteroatoms (B) is 30 ≤ α / β ≤ 95, and the curing agent having heteroatoms (B) comprises an amineimide compound represented by the following formula (1), formula (2), or formula (3). (In formulas (1) to (3), R1 each independently represents a hydrogen atom, or a monovalent or n-valent hydrocarbon group having 1 to 15 carbon atoms, a group in which a hydrogen atom bonded to a carbon atom in the hydrocarbon group is substituted by a hydroxyl group, or a group in which a portion of the carbon atoms constituting the hydrocarbon group is substituted by an ether bond; R2 and R3 each independently represent an unsubstituted or substituent alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a heterocyclic group having 7 or fewer carbon atoms selected from the azetidine ring, pyrrole ring, morpholine ring, thiazine ring, piperidine ring, hexamethyleneimine ring, and azepine ring connected by R2 and R3; R4 each independently represents a monovalent or n-valent organic group having 1 to 30 carbon atoms, which may include a hydrogen atom or an oxygen atom; and n represents an integer from 1 to 3.) Claim 2 An epoxy resin composition according to claim 1, wherein n in formula (2) or formula (3) is 2 or 3. Claim 3 An epoxy resin composition according to claim 1, further comprising (C) an inorganic filler. Claim 4 An epoxy resin composition according to claim 3, wherein the content of the inorganic filler (C) is greater than 5 mass% and less than or equal to 98 mass% with respect to the entire epoxy resin composition. Claim 5 An epoxy resin composition according to claim 1, further comprising (D) a stabilizer. Claim 6 An epoxy resin composition according to claim 5, wherein the above (D) stabilizer comprises a compound represented by the following formula (A) or (B). (In formula (A), R5 and R6 each independently represent a monovalent or n-valent organic group having 1 to 15 carbon atoms, which may have a hydrogen atom, or a hydroxyl group, a carbonyl group, an ester bond, or an ether bond, and n represents an integer from 2 to 3.) (In formula (B), R7 represents 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, and n represents an integer from 2 to 3.) Claim 7 An epoxy resin composition according to claim 5, wherein the content of the (D) stabilizer is 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the (A) epoxy resin. Claim 8 A cured product of an epoxy resin composition as described in any one of claims 1 to 7. Claim 9 A sealant comprising the cured material described in paragraph 8. Claim 10 In paragraph 9, a sealant that is a sealant for semiconductors. Claim 11 An adhesive comprising an epoxy resin composition as described in any one of claims 1 to 7. Claim 12 delete

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