Epoxy resin compositions, hardeners, sealants and adhesives

Abstract

The epoxy resin composition of the present invention contains (A) 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 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

[Technical Field]

[0001] This invention relates to an epoxy resin composition, a cured material, a sealing material, and an adhesive. [Previous Technology]

[0002] Epoxy resins have excellent properties in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesion, and therefore can be used in a wide range of applications such as coatings, electrical and electronic insulating materials, and adhesives.

[0003] Patent Document 1 below discloses a resin for semiconductor packaging. Currently, commonly used epoxy resin compositions are so-called two-component epoxy resin compositions in which an epoxy resin and a curing agent are mixed during use.

[0004] Two-component epoxy resin compositions can be cured at room temperature, but on the other hand, the epoxy resin and the hardener need to be stored separately, and the two need to be metered and mixed as needed before use, which makes storage or handling more complicated. In addition, due to the limited usable time, there are the following problems: it is impossible to mix in large quantities in advance, the frequency of mixing increases, and the efficiency cannot be avoided.

[0005] To address the problems of such two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed to date. For example, epoxy resin compositions obtained by incorporating a latent curing agent into an epoxy resin can be cited. Patent Document 2 discloses an epoxy resin composition using a liquid aromatic amine.

[0006] Furthermore, recent requirements for electronic devices involve miniaturization, high functionality, lightweighting, and multi-functionality. For example, in semiconductor chip packaging technology, there is a demand for further miniaturization, high density, and finer spacing of electrode pads and solder pads. Moreover, underfill adhesive is used to protect the bump connections and the circuit surfaces of the chip in the gap between the chip and the substrate. With the miniaturization of spacing, there is a need for an underfill adhesive that penetrates into narrower gaps and exhibits good adhesion. [Prior Art Documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent No. 6282515 [Patent Document 2] Japanese Patent Application Publication No. 2019-172738 [Summary of the Invention]

[0008] [Problem to be solved by the invention] As described above, for a potential curing agent constituting a liquid epoxy resin composition, it is required to take into account both good curing properties and storage stability after mixing with epoxy resin, and also good permeability and adhesion to narrow gaps in electronic components, dense fibers such as carbon fibers or glass fibers.

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

[0010] Patent Document 2 discloses an epoxy resin composition that uses liquid aromatic amine compounds as a curing agent, but in order to improve the storage stability and adhesion of the curing agent, additives need to be added, which has the problem of complicated storage or handling.

[0011] Therefore, the object of the present invention is to provide, in view of the above circumstances, an epoxy resin composition having good adhesion, a cured form of the above epoxy resin composition, a sealing material, and an adhesive. [Technical Means for Solving the Problem]

[0012] In order to solve the above-mentioned problems, the inventors conducted intensive research and found that an epoxy resin composition containing a specific curing agent, wherein the molecular weight and the number of heteroatoms in the structure of the curing agent are within a specific range, can solve the above-mentioned problems, thereby completing the present invention. That is, the present invention is as follows.

[0013] [1] 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 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. [2] The epoxy resin composition as described in [1] above, wherein the curing agent having heteroatoms (B) comprises an aminoimine compound represented by the following formula (1), formula (2) or formula (3).

[0014] [Chemical 1]

[0015] (In formulas (1) to (3), R1 independently represents a hydrogen atom, or an organic group with 1 to 15 carbon atoms having a valent or n-valent structure, which may have a hydroxyl, carbonyl, ester, or ether bond; R2 and R3 independently represent an alkyl, aryl, aralkyl group with 1 to 12 carbon atoms having an unsubstituted or substituted structure, or a heterocycle with 7 or fewer carbon atoms formed by the linkage of R2 and R3; R4 independently represents a hydrogen atom, or an organic group with 1 to 30 carbon atoms having a valent or n-valent structure, which may contain an oxygen atom; n represents an integer from 1 to 3)

[0016] [3] The epoxy resin composition described in [2] above, wherein n in formula (2) or formula (3) above is 2 or 3. [4] The epoxy resin composition described in any one of [1] to [3] above further includes (C) an inorganic filler. [5] The epoxy resin composition described in [4] above, wherein the content of the inorganic filler (C) above is more than 5% by mass and less than 98% by mass relative to the total epoxy resin composition. [6] The epoxy resin composition described in any one of [1] to [5] above further includes (D) a stabilizer. [7] The epoxy resin composition described in [6] above, wherein the stabilizer (D) above comprises a compound represented by formula (A) or (B) below.

[0017] [Chemical 2]

[0018] (In formula (A), R5 and R6 independently represent hydrogen atoms, or organic groups with 1 to 15 carbon atoms having a valence of one or n, such as hydroxyl, carbonyl, ester, or ether bonds, where n represents an integer of 2 to 3)

[0019] [Chemical 3]

[0020] (In formula (B), R7 represents an organic group with 1 to 15 carbon atoms that may have a hydroxyl, carbonyl, ester, or ether bond, or a monovalent or n-valent group, where n represents an integer of 2 to 3)

[0021] [8] The epoxy resin composition described in [6] or [7] above, wherein the content of the stabilizer in [D] above is more than 1 part by mass and less than 30 parts by mass relative to 100 parts by mass of the epoxy resin in [A] above. [9] A cured material, which is a cured material of the epoxy resin composition described in any one of [1] to [8] above.

[10] A sealing material comprising the cured material described in [9] above.

[11] The sealing material described in

[10] above is a sealing material for semiconductors.

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

[0022] According to the present invention, an epoxy resin composition having good adhesion, a cured form of the above epoxy resin composition, a sealing material and an adhesive can be provided.

Implementation Method

[0023] Hereinafter, embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail. Furthermore, this embodiment is an example for illustrating the present invention and does not limit the present invention to the following content. The present invention can be implemented with various changes within its scope.

[0024] [Epoxy Resin Composition] The epoxy resin composition of this embodiment contains: (A) epoxy resin and (B) a curing agent having heteroatoms (hereinafter, sometimes referred to as (B) curing agent), and the molecular weight α (hereinafter, sometimes simply referred to as "molecular weight α") of the curing agent having heteroatoms is 200≦α≦1200, and the ratio α / β of the molecular weight α to the number of heteroatoms β (hereinafter, sometimes simply referred to as "number of heteroatoms β") in the structure of the curing agent having heteroatoms is 30≦α / β≦95.

[0025] The epoxy resin composition of this embodiment exhibits excellent adhesion due to the aforementioned structure. This can be considered from the following perspectives, but is not limited to these factors. Specifically, it is believed that by having a molecular weight α of 200 or more for the hardener containing heteroatoms (B), the crosslinking length during curing increases, resulting in a strong and resilient structure. This suppresses the aggregation and destruction of the cured material, thus improving adhesion. On the other hand, it is believed that by having a molecular weight α of 1200 or less for the hardener containing heteroatoms (B), the dispersibility of the hardener (B) is excellent, allowing it to be sufficiently dispersed in the epoxy resin (A), thus achieving sufficient curing properties and resulting in sufficient adhesion. Furthermore, it is believed that by having a molecular weight α to the number of heteroatoms β in the structure of the hardener (B) ratio α / β of 95 or less, the number of polar functional groups in the hardener containing heteroatoms (B) increases, allowing the epoxy resin composition of this embodiment to firmly bond with the substrate through intermolecular bonds. On the other hand, it is believed that if the ratio of the molecular weight α to the number of heteroatoms β in the structure of the curing agent (B) having heteroatoms is 30 or more, the compatibility between the curing agent (B) and the epoxy resin (A) increases, which can make the epoxy resin composition fully cured, and thus sufficient adhesion can be obtained.

[0026] In the epoxy resin composition of this embodiment, the lower limit of the molecular weight α of the heteroatom-containing curing agent (B) is 200 or more, preferably 220 or more, and more preferably 250 or more. The upper limit of the molecular weight α of the heteroatom-containing curing agent (B) is 1200 or less, preferably 1100 or less, more preferably 1000 or less, and even more preferably 900. Furthermore, the molecular weight α of the heteroatom-containing curing agent (B) can be determined using an ESI-MS (Extraction, Analysis, and Measurement) device.

[0027] In the epoxy resin composition of this embodiment, the lower limit of the ratio α / β of the molecular weight α to the number of heteroatoms β in the structure of the heteroatom-containing curing agent (B) is 30 or more, preferably 35 or more, and more preferably 40 or more. The upper limit of the ratio α / β is 95 or less, preferably 90 or less, and more preferably 80 or less. The number of heteroatoms β in the structure of the heteroatom-containing curing agent (B) can be determined using an ESI-MS (Extraction, Analysis, and Measurement) apparatus. The number of heteroatoms β in the structure of the heteroatom-containing curing agent (B) is not particularly limited, but from the viewpoint of compatibility with the epoxy resin (A), it is preferably 5 or more and 25 or less, more preferably 5 or more and 20 or less, and even more preferably 5 or more and 15 or less. In the preparation step of the heteroatom-containing curing agent (B), the molecular weight α and the ratio α / β can be controlled within the above-mentioned numerical range by transforming the molecular structure through a chemical reaction.

[0028] (A) Epoxy Resin) The epoxy resin composition of this embodiment contains (A) epoxy resin. The (A) epoxy resin is not limited to the following, but examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, and diphenyl sulfide type epoxy resin. Epoxy resins include: esters, diphenyl sulfide type epoxy resins, diphenyl disulfide type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, hydroquinone type epoxy resins, methyl hydroquinone type epoxy resins, butyl hydroquinone type epoxy resins, resorcinol type epoxy resins, methyl resorcinol type epoxy resins, catechol type epoxy resins, N,N-diglycidyl aniline type epoxy resins, and ethylene oxide addition-type bisphenol A type epoxy resins. Difunctional epoxy resins include propylene oxide addition-cured bisphenol A type epoxy resins, ethylene oxide addition-cured bisphenol F type epoxy resins, and propylene oxide addition-cured bisphenol F type epoxy resins; triphenol type epoxy resins, N,N-diglycidylaminophenyl type epoxy resins, o-(N,N-diglycidylamino)toluene type epoxy resins, triphenol type epoxy resins, ethylene oxide addition-cured triphenol type epoxy resins, and propylene oxide addition-cured triphenol type epoxy resins, etc. Trifunctional epoxy resins; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resin and diaminobenzene type epoxy resin; polyfunctional epoxy resins such as phenol-formaldehyde varnish type epoxy resin, cresol-formaldehyde varnish type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, and brominated phenol-formaldehyde varnish type epoxy resin; and alicyclic epoxy resins. These can be used alone or in combination with two or more. Furthermore, they can also be used in combination with epoxy resins modified using isocyanates or the like. There are no particular limitations on the aforementioned epoxy resins; for example, bisphenol F type epoxy resin can be used alone, or a combination of bisphenol F type epoxy resin and bisphenol A type epoxy resin, or a combination of bisphenol F type epoxy resin and naphthyl type epoxy resin, etc., is suitable.

[0029] In the epoxy resin composition of this embodiment, the content of (A) epoxy resin is not particularly limited, but is preferably 60% by mass or more and 95% by mass or less, more preferably 65% ​​by mass or more and 90% by mass or less, and even more preferably 70% by mass or more and 85% by mass or less, relative to the liquid component of the epoxy resin composition. By keeping the content of (A) epoxy resin within the above range, it is likely to obtain higher adhesion.

[0030] ((B) Curing Agent Containing Heteroatoms) The epoxy resin composition of this embodiment includes (B) a curing agent containing heteroatoms. (B) The curing agent containing heteroatoms is a curing agent that satisfies the above-mentioned conditions of molecular weight α and ratio α / β. (B) The curing agent containing heteroatoms can be any agent containing heteroatoms and is not particularly limited, but preferably a curing agent containing heteroatoms in the main chain. Furthermore, the above-mentioned curing agent containing heteroatoms in the main chain is not particularly limited, but from the viewpoint of functioning as a potential curing agent, it is preferable to have a curing agent containing nitrogen atoms and oxygen atoms in the main chain, and more preferably a curing agent containing N-N bonds in the main chain. Regarding (B) the curing agent containing heteroatoms, from the viewpoint of functioning as a potential curing agent, for example, the following aminoimine compounds can be suitably used.

[0031] From the viewpoint that the epoxy resin composition of this embodiment has excellent permeability and excellent curing and storage stability, (B) the curing agent having heteroatoms is preferably an amino-imine compound represented by the following formula (1), (2) or (3) (hereinafter, sometimes referred to as "amino-imine compound in this embodiment").

[0032] [Chemical 4]

[0033] In formulas (1) to (3), R1 independently represents a hydrogen atom or an organic group with 1 to 15 carbon atoms having a monovalent or n-valent bond, which may have a hydroxyl group, carbonyl group, ester bond or ether bond; R2 and R3 independently represent an alkyl group, aryl group, aralkyl group with 1 to 12 carbon atoms having no substitution or a substituent group, or a heterocycle with 7 or fewer carbon atoms formed by the linkage of R2 and R3; R4 independently represents a hydrogen atom or an organic group with 1 to 30 carbon atoms having a monovalent or n-valent bond, which may contain an oxygen atom; n represents an integer from 1 to 3.

[0034] The amide-imine compound in this embodiment is preferably a liquid compound at room temperature. In this embodiment, the indicator "liquid at room temperature" can be the viscosity at 25°C. Furthermore, from the viewpoint of further improving the solubility or dispersibility in the epoxy resin composition of this embodiment and the permeability to the substrate, the viscosity of the amide-imine compound in this embodiment at 25°C is preferably 1300 Pa·s or less, more preferably 900 Pa·s or less, further preferably 800 Pa·s or less, and further preferably 700 Pa·s or less. Moreover, there is no particular limitation on the lower limit of the viscosity at 25°C, but it is preferably 0.01 Pa·s or more. The viscosity of the amide-imine compound in this embodiment can be controlled, for example, by adjusting the functional groups R1 to R4 in formulas (1) to (3). Furthermore, the viscosity (Pa·s) of the amide imine compound at 25°C in this embodiment can be measured by, for example, by adding approximately 0.3 mL of the amide imine compound to a measuring cup and measuring it using an E-type viscometer (TVE-35H manufactured by Toki Industrial Co., Ltd.) 15 minutes after the sample temperature reaches 25°C.

[0035] In the above formulas (2) and (3), n represents an integer from 1 to 3. From the viewpoint of the adhesion of the epoxy resin composition of this embodiment, n in the above formulas (2) and (3) is preferably 2 or 3.

[0036] In the above formulas (1), (2) and (3), R1 independently represents a hydrogen atom or "an organic group having 1 to 15 carbon atoms with a single or n valence, which may have a hydroxyl group, a carbonyl group or an ester bond". There is no particular limitation on such organic group, for example: "hydrocarbon group", "a group in which the hydrogen atom of the carbon atom bonded to the hydrocarbon group is replaced by a hydroxyl group or a carbonyl group", or "a group in which a portion of the carbon atom constituting the hydrocarbon group is replaced by an ester bond or an ether bond".

[0037] Examples of the above-mentioned hydrocarbon groups include: straight-chain, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octyynyl, decynyl, dodecynyl, hexadecynyl, and octadecynyl; aryl groups such as phenyl; and aralkyl groups containing combinations of alkyl and phenyl groups such as methylphenyl, ethylphenyl, and propylphenyl.

[0038] Furthermore, the organic group represented by R1 in the above formulas (1) to (3) may be unsubstituted or may have substituents. Substituents are not limited to the following, for example: halogen atom, alkoxy group, carbonyl group, cyano group, azo group, azido group, thiol group, sulfonyl group, nitro group, hydroxyl group, acetyl group, aldehyde group.

[0039] The number of carbon atoms in 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. By making the number of carbon atoms in the organic group represented by R1 within the above range, there is a tendency to further improve the curing properties of the amine imine compounds in the above formulas (1) to (3). Furthermore, by making the number of carbon atoms in the organic group represented by R1 within the above range, the ease of obtaining the raw materials used to prepare the above formulas (1) to (3) is further improved.

[0040] Preferably, the organic group represented by R1 in formula (1) or (3) is the group represented by formula (4) or (5) below. By having formula (1) or (3) have the group represented by formula (4) or (5) below as R1, there is a tendency to further improve the curing properties of the amine imine compound.

[0041] [Chemical 5]

[0042] In the above formulas (4) and (5), R11 independently represents an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an aryl group, or an aralkyl group with 7 to 9 carbon atoms, and n independently represents an integer from 0 to 6.

[0043] In formula (5) above, it is preferable that n is a base of 0 or 1. Thus, the amine imine compound represented by formula (1) or (3) above has a diketone structure in the R1-C(=O)- structure. This diketone structure tends to further enhance the hardening properties of the amine imine compound.

[0044] Furthermore, the number of carbons and n of R11 in the above formula (4) or (5) are adjusted so that the maximum number of carbons of the group represented by the above formula (4) or (5) does not exceed 15. Also, as examples of alkyl with 1 to 5 carbons, alkoxy with 1 to 5 carbons, aryl, or aralkyl with 7 to 9 carbons in R11, the same group as the organic group represented by R1 above can be cited.

[0045] Furthermore, the organic group represented by R1 in the above formula (2) is preferably the group represented by formula (6) or (7) below. By making the above formula (2) have the group represented by formula (6) or (7) below as R1, it is easy to obtain an aminoimide compound that is liquid at room temperature, and there is a tendency to further improve the curing properties of the aminoimide compound.

[0046] [Chemical 6]

[0047] In the above formulas (6) and (7), R12 and R13 independently represent a single bond, an alkyl group with 1 to 5 carbon atoms, an aryl group, or an aralkyl group with 7 to 9 carbon atoms.

[0048] In formula (7) above, R13 is preferably a single bond or a methyl group. Therefore, the amine imine compound represented by formula (2) above has a diketone structure in the R1-C(=O)- structure. This diketone structure tends to further enhance the hardening properties of the amine imine compound. Furthermore, examples of alkyl, aryl, or aralkyl groups with 1 to 5 carbon atoms in R12 and R13 can be the same groups shown in the organogroup represented by R1 above.

[0049] In the above formulas (1), (2) and (3), R2 and R3 independently represent alkyl, aryl, aralkyl, or heterocyclic rings with 1 to 12 carbon atoms that have not been substituted or have substituents, or alkyl rings with 7 or fewer carbon atoms formed by the linkage of R2 and R3.

[0050] The alkyl group represented by R2 or R3, having 1 to 12 carbon atoms, is not limited to the following, but may include, for example, straight-chain alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched alkyl groups such as isopropyl, isobutyl, tributyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl. Furthermore, the aforementioned alkyl groups may also be combinations of straight-chain or branched alkyl groups with cyclic alkyl groups. Moreover, the aforementioned alkyl groups may also contain unsaturated bonded groups.

[0051] 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 a processability point of view, it is preferable to set the number of carbon atoms in the alkyl group represented by R2 or R3 to 2 or more. Furthermore, by setting the number of carbon atoms in the alkyl group represented by R2 or R3 to 5 or more, it is easy to obtain an aminoimide compound that is liquid at room temperature, and there is a tendency to further improve the curing properties of the aminoimide compound.

[0052] Furthermore, the aryl group represented by R2 or R3 is not limited to the following, for example, phenyl or naphthyl. Furthermore, the aralkyl group represented by R2 or R3 is not limited to the following, for example, methylphenyl, ethylphenyl, methylnaphthyl, or dimethylnaphthyl. Preferably, at least one of R2 and R3 is an aralkyl group, more preferably methylphenyl (benzyl). This tends to further improve the curing properties of the amineimide compound. Moreover, the number of carbon atoms of the aryl group and aralkyl group represented by R2 or R3 is not particularly limited, but is preferably 6 to 20.

[0053] The substituents of alkyl, aryl or aralkyl represented by R2 or R3 are not limited to the following, for example: halogen atom, alkoxy, carbonyl, cyano, azo, azido, thiol, sulfonyl, nitro, hydroxyl, acetyl, aldehyde.

[0054] R2 and R3 can also be linked to form a heterocycle with 7 or fewer carbon atoms. Such a heterocycle is not limited to the following, for example, the heterocycle formed by R23 and N+ in formula (1), (2) or (3) can be exemplified by the following formula (8). Furthermore, R23 represents a base formed by linking R2 and R3.

[0055] [Chemical 7]

[0056] In Equation (8), R23 represents the basis that forms a heterocyclic structure together with N+.

[0057] The heterocycle formed by R23 and N+ is not limited to the following, for example: four-membered rings such as acridine ring; five-membered rings such as pyrrolidine ring, pyrrole ring, α-porphyrin ring, thiazoline ring; six-membered rings such as piperidine ring; seven-membered rings such as hexamethyleneimine ring, nitropyridine ring, etc.

[0058] Among these, the heterocyclic rings are preferably pyrrole rings, α-porphyrin rings, thiazoline rings, piperidine rings, hexamethyleneimine rings, and nitropyridine rings, and more preferably six-membered and seven-membered rings. By having such a group, it is easy to obtain aminoimine compounds that are liquid at room temperature, and there is a tendency to further improve the hardening properties of aminoimine compounds.

[0059] Furthermore, the substituents present in the heterocycle that is linked and has 7 or fewer carbon atoms are not limited to the following, for example: alkyl, aryl, or the substituents in R2 and R3 mentioned above. Moreover, when the heterocycle has an alkyl group as a substituent, examples include methyl groups bonded to the carbon atom adjacent to N+.

[0060] In the above formulas (1), (2) and (3), R4 independently represents a hydrogen atom or "an organic group with 1 to 30 carbon atoms, which may contain oxygen atoms, and has a monovalent or n-valent charge." Such an organic group is not limited to the following, but may include, for example, "hydrocarbon group", "a group in which the hydrogen atom of the carbon atom bonded to the hydrocarbon group is replaced by a hydroxyl group, a carbonyl group, or a group containing a silicon atom", or "a group in which a portion of the carbon atom constituting the hydrocarbon group is replaced by an ester bond or an ether bond, or a silicon atom".

[0061] The hydrocarbon group represented by R4 is not limited to the following, but may include, for example: straight-chain, branched or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octyynyl, decynyl, dodecaynyl, hexadecynyl, octadecynyl; aryl groups such as phenyl; or aralkyl groups containing combinations of alkyl and phenyl groups such as methylphenyl, ethylphenyl, propylphenyl.

[0062] Furthermore, the hydrocarbon group represented by R4 includes bisphenol skeletons such as bisphenol A type skeleton, bisphenol AP type skeleton, bisphenol B type skeleton, bisphenol C type skeleton, bisphenol E type skeleton, and bisphenol F type skeleton. As an organic group containing a bisphenol skeleton, it is not limited to the following, for example, a group formed by adding polyoxyalkylene to the hydroxyl group of each bisphenol skeleton.

[0063] Wherein, the organic group represented by R4 in the above formula (1) or (2) is preferably alkyl, alkenyl, or aralkyl, more preferably alkyl or alkenyl, and even more preferably branched alkyl or branched alkenyl. Furthermore, these preferred groups may have substituents. By having such groups, there is a tendency to further improve the curing properties of the amide imine compound. Also, there is a tendency to further increase the glass transition temperature (Tg) of the cured product obtained using the amide imine compound.

[0064] 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. By ensuring that the number of carbon atoms in the organic group represented by R4 is within the above range, there is a tendency to further improve the curing properties of the amide imine compound. Furthermore, the Tg of the cured product obtained using the amide imine compound is further improved, and furthermore, by ensuring that the number of carbon atoms in the organic group represented by R4 is within the above range, the availability of raw materials for preparing the amide imine compound is further improved.

[0065] Wherein, R4 in formula (1) or (2) above is preferably a linear or branched alkyl group having 3 to 12 carbon atoms, or a linear or branched alkenyl group having 3 to 6 carbon atoms. By having such a group, there is a tendency to further improve the curing properties of the amide imine compound.

[0066] Furthermore, R4 in the above formula (3) is preferably a base represented by formula (9) or (10) below. By having a base represented by formula (9) or (10) below as R4 in the above formula (3), there is a tendency to further improve the curing properties of the amide imine compound.

[0067] [Chemical 8]

[0068] In formulas (9) and (10), R41 and R42 independently represent alkyl, aryl, or aralkyl groups with 1 to 5 carbon atoms, and n independently represents an integer from 0 to 10.

[0069] The epoxy resin composition of this embodiment may also contain a plurality of amine imine compounds represented by formulas (1), (2) or (3) above as curing agents. By containing a plurality of amine imine compounds, curing temperature control or viscosity control can be achieved, thereby obtaining a property improvement effect. Furthermore, the epoxy resin composition of this embodiment may also contain a plurality of amine imine compounds represented by formulas (1) to (3) above, of which amine imine compounds are represented by the same formula but have different structures.

[0070] When using an aminoimide composition containing a plurality of aminoimide compounds as (B) a curing agent having heteroatoms, the aminoimide composition can be obtained by mixing a plurality of aminoimide compounds, or by simultaneously manufacturing a plurality of aminoimide compounds in the following method for manufacturing aminoimide compounds.

[0071] <Method for manufacturing aminoimine compounds and aminoimine compositions> The method for manufacturing the aminoimine compound (B) which is a heteroatom-containing curing agent used in the epoxy resin composition of this embodiment is not particularly limited, as long as it is a method that can obtain an aminoimine compound having any of the structures of formulas (1) to (3) above. The method for manufacturing the aminoimine composition includes the following methods: a method for mixing a plurality of aminoimine compounds obtained by the following methods; and a method for simultaneously manufacturing a plurality of amine compounds to obtain a mixture.

[0072] Regarding the method for manufacturing aminoimine compounds, as an example, a method having the following reaction steps can be cited, in which an ester compound (BA), a hydrazine compound (BB), and a glycidyl ether compound (BC) are reacted. The method for manufacturing aminoimine compounds will be described below. Furthermore, the compounds (BA) to (BC) will sometimes be referred to as "(BA) components, etc."

[0073] As an ester compound (BA), it is not limited to the following, for example, monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, or cyclic esters can be cited. As a monocarboxylic acid ester compound, it is not limited to the following, for example, methyl lactate, ethyl lactate, methyl amygdalinate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl trimethylacetate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl butenoate, methyl isobutenoate, methyl benzoate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-tert-butoxybenzoylmethyl, etc. Furthermore, ethyl esters, propyl esters, etc., can also be used instead of these. As dicarboxylic acid ester compounds, the following are not limited to: dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl heptaate, dimethyl octanoate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-propanone dicarboxylate, and diethyl 1,3-propanone dicarboxylate. Cyclic esters may also be used instead. Cyclic esters are not limited to: α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, etc. Alternatively, diethyl esters, dipropyl esters, etc., can be used as substitutes.

[0074] Among these, from the viewpoint of the curing properties and liquefaction of the amine imine compound as the (B) curing agent, the ester compound (BA) is preferably ethyl lactate, methyl amygdalin, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl trimethylacetate, methyl acrylate, methyl methacrylate, methyl butyl acrylate, methyl isobutyl acrylate, methyl benzoate, and methyl benzoate. Dimethyl phthalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl heptaate, dimethyl octanoate, dimethyl azelaate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-propanone dicarboxylate, and diethyl 1,3-propanone dicarboxylate, γ-butyrolactone, δ-valerolactone, and γ-valerolactone.

[0075] Furthermore, from the viewpoint of ease of acquisition, the ester compound (BA) is preferably ethyl lactate, ethyl propionate, methyl amygdalin, methyl benzoate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and diethyl 1,3-acetone dicarboxylate. One ester compound (BA) may be used alone, or two or more may be used in combination.

[0076] As a hydrazine compound (BB), it is not limited to the following, 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-aminohopiperidine, 1-amino-2,6-dimethylpiperidine, 1-aminopyrrolidine, 1-amino-2-methylpyrrolidine, 1-amino-2-phenylpyrrolidine and 1-aminopyrrolidine, etc.

[0077] From the viewpoint of curability and liquefaction, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminopyrrolidine are preferred as hydrazine compounds (BB). Furthermore, from the viewpoint of ease of acquisition and safety, dibenzylhydrazine and 1-aminopiperidine are more preferred. A single hydrazine compound (BB) may be used, or two or more may be used in combination.

[0078] The glycidyl ether compound (BC) is not limited to the following, for example, a monofunctional monoglycidyl ether compound or a difunctional or higher polyglycidyl ether compound can be used. The monoglycidyl ether compound is not limited to the following, for example: methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, tributyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, o-phenylphenol glycidyl ether, benzyl glycidyl ether, biphenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, tributyldimethylsilyl glycidyl ether, 3-[diethoxy(methyl)silyl]propyl glycidyl ether, etc. As a polyglycidyl ether compound, it is not limited to the following, but examples include: ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether. Aliphatic polyglycidyl ethers such as diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether; alicyclic polyglycidyl ether compounds such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, ethylene oxide addition-type bisphenol A type diglycidyl ether, propylene oxide addition-type bisphenol A type diglycidyl ether, and hydrides of their condensates; aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether, etc.

[0079] Among these, from the viewpoint of the curing properties and liquefaction of the amine imine compound as (B) curing agent, the preferred glycidyl ether compound (BC) is methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, tributyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, tributyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, ethylene oxide addition type bisphenol A type diglycidyl ether, and propylene oxide addition type bisphenol A type diglycidyl ether.

[0080] Furthermore, from the viewpoint of ease of acquisition and Tg of the hardened product, the glycidyl ether compound (BC) is preferably n-butyl glycidyl ether, tributyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, trimethylolpropane polyglycidyl ether, ethylene oxide addition-type bisphenol A diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, and propylene oxide addition-type bisphenol A diglycidyl ether. One glycidyl ether compound (BC) may be used alone, or two or more may be used in combination.

[0081] The amounts of ester compound (BA), hydrazine compound (BB), and glycidyl ether compound (BC) added to the reaction system for preparing the aminoimine compound can be set based on the mol ratio of functional groups. Relative to 1 mol of a primary amine of the hydrazine compound (BB), the ester group of the ester compound (BA) is preferably 0.8 mol to 3.0 mol, more preferably 0.9 mol to 2.8 mol, and even more preferably 0.95 mol to 2.5 mol. Furthermore, relative to 1 mol of a primary amine of the hydrazine compound (BB), the glycidyl group of the glycidyl ether compound (BC) is preferably 0.8 mol to 2.0 mol, more preferably 0.9 mol to 1.5 mol, and even more preferably 0.95 mol to 1.4 mol.

[0082] By controlling the amount of glycidyl group of glycidyl ether compound (BC) relative to 1 mol of a primary amine of hydrazine compound (BB), an aminoimine composition comprising the aminoimine compounds represented by formulas (1) and (3) above can be simultaneously manufactured. Specifically, the amount of glycidyl group of glycidyl ether compound (BC) relative to 1 mol of a primary amine of hydrazine compound (BB) is preferably 0.1 mol to 3.0 mol, more preferably 0.3 mol to 2.0 mol, and even more preferably 0.5 mol to 1.0 mol.

[0083] In the above-mentioned methods for manufacturing aminoimine compounds and aminoimine compositions, from the viewpoint of ensuring uniform reaction, a solvent may also be used.

[0084] The solvent does not need to react with the above (BA) to (BC) components, and there are no particular limitations. Examples include: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and tributanol; ethers such as tetrahydrofuran and diethyl ether.

[0085] The reaction temperature of the above-mentioned (BA) to (BC) components is preferably 10 to 100°C, and more preferably 40 to 90°C. By setting the reaction temperature to 10°C or higher, the reaction progresses faster, and the purity of the obtained amide imine compound tends to be further improved. Furthermore, by setting the reaction temperature to 90°C or lower, the polymerization reaction between glycidyl ether compounds (BC) can be suppressed efficiently, thus tending to further improve the purity of the amide imine compound.

[0086] The reaction time for the above-mentioned (BA) to (BC) components is preferably 1 hour to 168 hours, more preferably 1 hour to 96 hours, and even more preferably 1 hour to 48 hours.

[0087] After the reaction is complete, the obtained reactants can be purified by known purification methods such as washing, extraction, recrystallization, and column chromatography. For example, after washing the reaction solution containing dissolved organic solvent with water, the organic layer can be heated under normal or reduced pressure to remove unreacted raw materials or organic solvents from the reaction solution and recover the amide imine compound. Alternatively, column chromatography can be used for purification to recover the amide imine compound.

[0088] The solvent used for the above cleaning can dissolve the residue of the raw material and is not particularly limited. From the point of view of yield, purity and ease of removal, 1-hexane, 1-pentane and cyclohexane are preferred.

[0089] The organic solvent used in the above extraction can dissolve the target amine imine compound, and there is no particular limitation. From the point of view of yield, purity and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are even more preferred.

[0090] The packing material used in column chromatography can be alumina, silicone, or other known materials. The developing solvent can be ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, or other known materials, either alone or in combination.

[0091] <Heteroatom-containing curing agent (B) other than amine-imine compounds> Regarding the epoxy resin composition of this embodiment, as the heteroatom-containing curing agent (B), any heteroatom-containing curing agent other than amine-imine compounds can be used, as long as the molecular weight and the number of heteroatoms in the structure of the curing agent are within a specific range. Such heteroatom-containing curing agents are not limited to the following, but may include, for example: amine curing agents such as imidazoles, aliphatic amines, aromatic amines, and polyamine resins; amine curing agents; acid anhydrides; phenolic curing agents such as phenols, polyphenol compounds and their modified forms; BF3-amine complexes; guanidine derivatives, etc. One of these curing agents may be used alone, or two or more may be used in combination.

[0092] <(B) Content of Heteroatom-Containing Hardener> In the epoxy resin composition of this embodiment, relative to 100 parts by mass of the total amount of epoxy resin (A), the total content of (B) heteroatom-containing hardener 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. By keeping the total content of (B) heteroatom-containing hardener within the above range, the curing reaction of the epoxy resin composition of this embodiment is sufficiently promoted, and there is a tendency to obtain better curing properties. Furthermore, in the epoxy resin composition of this embodiment, when the above-mentioned amine imine compound is used as a hardener, the total content of the above-mentioned amine imine compound is, as above, relative to 100 parts by mass of the total amount of epoxy resin (A), 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. By keeping the total content of the amide-imide compound in this embodiment within the aforementioned range, the curing reaction of the epoxy resin composition is sufficiently promoted, and there is a tendency to obtain better cured properties. Furthermore, when using the amide-imide compound in this embodiment as a curing accelerator for a heteroatom-containing curing agent (B) other than the amide-imide compound, the total content of the amide-imide compound in this 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, relative to 100 parts by mass of the total amount of epoxy resin (A). By keeping the content of the amide-imide compound in this embodiment within the aforementioned range, it functions as a curing catalyst for the heteroatom-containing curing agent (B) other than the amide-imide compound in this embodiment, sufficiently promoting the curing reaction, and there is a tendency to obtain better cured properties.

[0093] In the epoxy resin composition of this embodiment, (B) a heteroatom-containing curing agent and other curing agents besides (B) can be used together. In this case, (B) a heteroatom-containing curing agent can function as a curing accelerator for the other curing agents. When (B) a heteroatom-containing curing agent and other curing agents are used together, the total content of (B) a heteroatom-containing curing agent 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, relative to 100 parts by mass of epoxy resin (A). When used together with other curing agents, by keeping the content of (B) a heteroatom-containing curing agent within the above range, it functions as a curing catalyst for the other curing agents, fully promoting the curing reaction, and tends to obtain better cured properties.

[0094] Other curing agents besides the curing agent (B) that can be used in conjunction with curing agents having heteroatoms are not limited to the following, for example: amine curing agents such as imidazoles, aliphatic amines, aromatic amines, and polyamide resins that do not satisfy the above molecular weight α and ratio α / β; amide curing agents; acid anhydride curing agents; phenolic curing agents such as phenols, polyphenol compounds and their modified forms; BF3-amine complexes; guanidine derivatives, etc. One of these other curing agents may be used alone, or two or more may be used in combination.

[0095] Furthermore, in the epoxy resin composition of this embodiment, from the viewpoint of balancing reactivity and stability, the total content of (B) the curing agent having heteroatoms in the epoxy resin composition is preferably 0.4% to 50% by mass. From the viewpoint of reactivity, it is more preferably 2.0% by mass or more, and even more preferably 8.1% by mass or more, and even more preferably 9.0% by mass or more. Furthermore, from the viewpoint of maintaining stability, it is more preferably 40% by mass or less, and even more preferably 25% by mass or less, and even more preferably 22% by mass or less.

[0096] ((C) Inorganic filler) The epoxy resin composition of this embodiment may also contain an inorganic filler as needed. By using an inorganic filler, the low thermal expansion of the obtained cured product can be improved. There are no particular limitations on the inorganic filler, and examples include: fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride, etc.

[0097] In the epoxy resin composition of this embodiment, the content of (C) inorganic filler is preferably more than 5% by mass and less than 98% by mass, more preferably more than 10% by mass and less than 95% by mass, further preferably more than 10% by mass and less than 90% by mass, and further preferably more than 10% by mass and less than 87% by mass. By keeping the content of (C) inorganic filler within the above range, it is likely to obtain a cured product with low thermal expansion.

[0098] ((D) Stabilizer) The epoxy resin composition of this embodiment may also contain a (D) stabilizer if necessary. As a (D) stabilizer, it is not limited to the following, for example: monocarboxylic acid ester compounds, dicarboxylic acid ester compounds or cyclic lactone compounds.

[0099] The stabilizer described above may, for example, be a compound represented by the following formula (A) or (B).

[0100] [Chemical 9]

[0101] In formula (A), R5 and R6 independently represent hydrogen atoms or organic groups with 1 to 15 carbon atoms, which may have hydroxyl, carbonyl, ester or ether bonds, and n represents an integer from 2 to 3.

[0102] [Chemical 10]

[0103] In formula (B), R7 represents an organic group with 1 to 15 carbon atoms that may have a valent or n-valent group, such as a hydroxyl group, carbonyl group, ester bond or ether bond, and n represents an integer from 2 to 3.

[0104] In the above formula (A), R5 and R6 independently represent a hydrogen atom or "an organic group having 1 to 15 carbon atoms with a monovalent or n-valent charge, which may have a hydroxyl, carbonyl, or ester bond". Furthermore, in the above formula (B), R7 represents "an organic group having 1 to 15 carbon atoms with a monovalent or n-valent charge, which may have a hydroxyl, carbonyl, ester, or ether bond". Such organic groups are not limited to the following, for example: "hydrocarbon group" which is the same as R1 in the above formula (1), "a group in which the hydrogen atom of the carbon atom bonded to the hydrocarbon group is replaced by a hydroxyl or carbonyl group", or "a group in which part of the carbon atom constituting the hydrocarbon group is replaced by an ester or ether bond".

[0105] Regarding the monocarboxylic acid ester compounds used as stabilizers in (D) above, they are not limited to the following, but may include, for example: methyl lactate, ethyl lactate, methyl amygdalinate, methyl acetate, methyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl trimethylacetate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl butenoate, methyl isobutenoate, methyl benzoate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-tert-butoxybenzoylmethyl, etc. Furthermore, ethyl esters, propyl esters, etc., may also be used instead.

[0106] The dicarboxylic acid ester compounds used as stabilizers in (D) above are not limited to the following, but may include, for example: dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl heptaate, dimethyl octanoate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-propanone dicarboxylate, and diethyl 1,3-propanone dicarboxylate, etc.

[0107] Regarding the cyclic ester compounds used as stabilizers in (D) above, they are not limited to the following, but may include, for example, α-acetyl lactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, etc. Furthermore, diethyl esters, dipropyl esters, etc., may also be used instead.

[0108] The epoxy resin composition of this embodiment may also use other stabilizers besides the stabilizers described above. Other stabilizers are not limited to the following, but may include, for example, Lewis acid compounds containing boron, aluminum, gallium, indium, etc., or acidic compounds such as carboxylic acids, phenols, organic acids, etc.

[0109] In the epoxy resin composition of this embodiment, the content of stabilizer (D) 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, relative to 100 parts by mass of epoxy resin (A). By keeping the content of stabilizer (D) within the above range, it is likely to obtain an epoxy resin composition with excellent storage stability.

[0110] (Other Composite Agents) The epoxy resin composition of this embodiment may further contain other composite agents such as curing accelerators, flame retardants, silane coupling agents, release agents, and pigments, as needed. These can be appropriately selected as long as they are within the range that achieves the effects of this embodiment. As for flame retardants, they are not limited to the following, but may include, for example, halides, compounds containing phosphorus atoms, compounds containing nitrogen atoms, and inorganic flame retardant compounds.

[0111] [Preparation of Epoxy Resin Composition and Cured Product] The cured product of this embodiment is a cured product obtained by curing the epoxy resin composition of this embodiment described above. The cured product of this embodiment can be obtained by heat curing the epoxy resin composition, for example, by a previously known method. For example, the cured product of this embodiment can be obtained by the following method. First, the epoxy resin (A), the curing agent having heteroatoms (B), and (C) inorganic filler (D), stabilizer, curing accelerator and / or composite agent (added as needed) are thoroughly mixed to homogeneity using an extruder, kneader, roller, etc., to obtain an epoxy resin composition. Then, the epoxy resin composition is cast or molded using a transfer molding machine, compression molding machine, injection molding machine, etc., and then heated at a temperature of about 80 to 200°C for about 2 to 10 hours to obtain the cured product of this embodiment.

[0112] Furthermore, the cured product of this embodiment can be obtained, for example, by the following method. First, the above-mentioned epoxy resin composition is dissolved in solvents such as toluene, xylene, acetone, methyl ethyl ketone, and methyl isobutyl ketone to obtain a solution. The obtained solution is then impregnated with a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg. Subsequently, the obtained prepreg is hot-pressed to obtain a cured product.

[0113] [Applications] The epoxy resin composition of this embodiment and the cured product obtained therefrom can be used in various applications where epoxy resin is used as a material. In particular, it is especially useful as a sealing material (a sealing material formed from the cured product of this embodiment), a semiconductor sealing material, an adhesive (an adhesive containing the epoxy resin composition of this embodiment), a printed circuit board material, a coating, and a composite material. Among these applications, it is suitable for use as a semiconductor sealing material such as an underfill adhesive or molding compound, a conductive adhesive such as anisotropic conductive film (ACF), a printed wiring board such as a solder resist or cover lay film, and a composite material such as a prepreg impregnated with glass fiber or carbon fiber.

[0114] (Electronic Components) Electronic components can be manufactured using the cured material of this embodiment described above. The electronic components described above are not limited to the following; examples include: semiconductor sealing materials such as underfill adhesives or molding compounds; conductive adhesives such as ACF; printed circuit boards such as solder resists or cover films; and composite materials such as prepregs impregnated with glass fibers or carbon fibers. [Example]

[0115] Secondly, the present invention will be described in more detail through synthetic examples, embodiments and comparative examples, but the present invention is not limited in any way. Furthermore, unless otherwise specified, "parts" and "%" are used as mass measurements.

[0116] [(B) Synthesis of a curing agent with heteroatoms] An amino-imine compound having heteroatoms as (B) was synthesized. Subsequently, the molecular weight (molecular weight α) of the amino-imine compound and the number of heteroatoms β of the above-mentioned amino-imine compound were determined by ESI-MS, confirming that the target amino-imine compound could be synthesized.

[0117] [Synthesis Example 1] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound A (hereinafter compound A): 15.85 g (yield 92.2%). The ESI-MS value was 575.36 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0118] [Chemical 11]

[0119] [Synthesis Example 2] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound B (hereinafter compound B): 14.03 g (yield 86.4%). The ESI-MS value was 543.42 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0120] [Chemistry 12]

[0121] [Synthesis Example 3] 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. The solution was stirred at 80°C for 4 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound C (hereinafter compound C): 15.57 g (yield 86.2%). The ESI-MS value was 603.43 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0122] [Chemistry 13]

[0123] [Synthetic Example 4] 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. The solution was stirred at 80°C for 4 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound D (hereinafter compound D): 16.08 g (yield 85.1%). The ESI-MS value was 631.46 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0124] [Chemical 14]

[0125] [Synthesis Example 5] 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 epoxy resin (EXA850CRP, DIC Corporation) were mixed. The solution was stirred at 80°C for 4 hours to allow the reaction to proceed. The resulting reaction solution was concentrated under reduced pressure at 60°C, and by-product alcohols and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow compound E (hereinafter compound E): 18.64 g (yield 90.6%). The ESI-MS value was 685.44 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0126] [Chemistry 15]

[0127] [Synthesis Example 6] 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 glycidylamine compound (jER630, Mitsubishi Chemical Corporation) were mixed. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by-product alcohols and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow compound F (hereinafter compound F): 14.18 g (yield 89.1%). The ESI-MS value was 794.45 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0128] [Chemistry 16]

[0129] [Synthesis Example 7] 9.83 g (0.060 mol) of methyl benzoate, 6.00 g (0.060 mol) of 1-aminopiperidine, and 11.16 g (0.060 mol) of 2-ethylhexyl glycidyl ether were mixed. The solution was stirred at 80°C for 4 hours to allow the reaction to proceed. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound G (hereinafter compound G): 23.82 g (yield 94.9%). The ESI-MS value was 419.31 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0130] [Chemistry 17]

[0131] [Synthesis Example 8] 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-butyl glycidyl ether were mixed. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound H (hereinafter compound H): 14.94 g (yield 94.9%). The ESI-MS value was 287.27 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0132] [Chemical 18]

[0133] [Synthesis Example 9] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound I (hereinafter compound I): 17.62 g (yield 89.3%). The ESI-MS value was 659.36 (H+), therefore the value corresponding to the molecular weight α in the table was used.

[0134] [Chemical 19]

[0135] [Synthesis Example 10] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound J (hereinafter compound J): 22.49 g (yield 89.5%). The ESI-MS value was 839.57 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0136] [Chemical 20]

[0137] [Synthesis Example 11] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction solution was concentrated under reduced pressure at 60°C, and by-product alcohols and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was concentrated again under reduced pressure at 60°C to obtain a pale yellow liquid compound K (hereinafter compound K): 24.29 g (yield 85.4%). The ESI-MS value was 811.51 (H+), therefore the value recorded in the table corresponding to the molecular weight α was used.

[0138] [Chemistry 21]

[0139] [Synthesis Example 12] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction solution was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound L (hereinafter compound L): 14.82 g (yield 83.7%). The ESI-MS value was 591.38 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0140] [Chemistry 22]

[0141] [Synthesis Example 13] 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 Bis(bisphenol) F type epoxy resin were mixed. The solution was stirred at 80°C for 4 hours to allow the reaction to proceed. The resulting reaction solution was concentrated under reduced pressure at 60°C, and by-product alcohols and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound M (hereinafter compound M): 17.00 g (yield 86.9%). The ESI-MS value was 653.43 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0142] [Chemistry 23]

[0143] [Synthesis Example 14] 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. The solution was stirred at 80°C for 4 hours to allow the reaction to proceed. The resulting reaction solution was concentrated under reduced pressure at 60°C, and by-product alcohols and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound N (hereinafter compound N): 15.35 g (yield 82.0%). The ESI-MS value was 625.40 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0144] [Chemical 24]

[0145] [Synthesis Example 15] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction solution was concentrated under reduced pressure at 60°C, and by-product alcohols and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was concentrated again under reduced pressure at 60°C to obtain a pale yellow liquid compound O (hereinafter compound O): 15.90 g (yield 86.6%). The ESI-MS value was 613.43 (H+), therefore the value corresponding to the molecular weight α in the table was used.

[0146] [Chemistry 25]

[0147] [Synthesis Example 16] 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. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction solution was concentrated under reduced pressure at 60°C, and by-product alcohols and unreacted starting materials were removed by distillation to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was concentrated again under reduced pressure at 60°C to obtain a pale yellow liquid compound P (hereinafter compound P): 15.38 g (yield 87.8%). The ESI-MS value was 585.38 (H+), therefore the value corresponding to the molecular weight α in the table is used.

[0148] [Chemistry 26]

[0149] [Synthesis Example 17] 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 tolyl glycidyl ether were mixed. The solution was stirred at 80°C for 4 hours while the reaction proceeded. The resulting reaction mixture was concentrated under reduced pressure at 60°C, and by distillation, byproducts of alcohol and unreacted starting materials were removed to obtain a liquid product. The product was repeatedly washed with hexane to remove unreacted starting material residues. The organic layer was again concentrated under reduced pressure at 60°C to obtain a pale yellow liquid compound Q (hereinafter compound Q): 8.13 g (yield 84.8%). The ESI-MS value was 321.42 (H+), therefore the value corresponding to the molecular weight α in the table was used.

[0150] [Chemistry 27]

[0151] Subsequently, epoxy resin compositions comprising the compounds of each synthesis example were prepared according to the following examples. Then, the following properties were measured for the obtained epoxy resin compositions.

[0152] [(1) Shear Bond Strength] Test pieces were prepared according to JISK6850 using the epoxy resin compositions of the examples and comparative examples described below. The adherend used was a cold-rolled copper plate with a width of 25 mm × length of 100 mm × thickness of 1.6 mm, according to JISC3141. Uncured test pieces were added to a small high-temperature chamber "ST-110B2" manufactured by ESPEC Co., Ltd., with an internal temperature stabilized at 150°C, and heated for 2 hours to obtain a shear bond strength test piece. After 2 hours, the structure (shear bond strength test piece) was removed from the small high-temperature chamber and placed at room temperature to cool to room temperature. After cooling to room temperature, the maximum load that caused the test piece to separate due to adhesive surface fracture was measured using an "AGX-5 kNX" manufactured by Shimadzu Corporation at a load cell speed of 5 kN and 5 mm / min. The value obtained by dividing the maximum load causing separation by the adhesive area was taken as the shear bond strength. "Adhesion" is evaluated based on the obtained shear bond strength according to the following criteria.

[0153] [Benchmark] ◎: Shear bond strength A is 16.0 MPa < A. 〇: Shear bond strength A is 13.5 MPa < A ≦ 16.0 MPa. △: Shear bond strength A is 10.0 MPa < A ≦ 13.5 MPa. ×: Shear bond strength A is A ≦ 10 MPa.

[0154] [(2) Storage stability] The epoxy resin compositions obtained in the following examples and comparative examples were stored at 25°C for 72 hours, and the viscosity before and after storage was measured using a BM type viscometer (25°C). The ratio of the viscosity of the epoxy resin composition after storage to the viscosity of the epoxy resin composition before storage (viscosity increase ratio) (=viscosity after storage / viscosity before storage) was calculated, and the "storage stability (storage stability at room temperature)" was evaluated based on the following criteria.

[0155] ◎: Viscosity increase ratio is less than 1.75 times. 〇: Viscosity increase ratio is more than 1.75 times but less than 3 times. ×: Viscosity increase ratio is more than 3 times.

[0156] [(3) Thermal expansion] The epoxy resin composition obtained in the following examples and comparative examples was added to a small high-temperature chamber "ST-110B2" manufactured by ESPEC Co., Ltd., whose internal temperature is stable at 150°C, and heated for 2 hours to obtain a hardened material for TMA (thermomechanical analysis) measurement. After 2 hours, the construct was removed from the small high-temperature chamber and placed at room temperature to cool to room temperature. After cooling to room temperature, TMA measurement was performed using a "Q400" manufactured by TA Instruments Co., Ltd., at a heating rate of 5°C / min. The value obtained by dividing the slope connecting the two points of 30°C and 45°C by the length of the test piece was used as the "coefficient of thermal expansion". Thermal expansion was evaluated based on the following criteria.

[0157] ◎: Coefficient of thermal expansion is less than 50 ppm / ℃. 〇: Coefficient of thermal expansion is 50 ppm / ℃ or higher but less than 70 ppm / ℃. △: Coefficient of thermal expansion is 70 ppm / ℃ or higher but less than 100 ppm / ℃. ×: Coefficient of thermal expansion is 100 ppm / ℃ or higher. Or it cannot be determined.

[0158] [Example 1] 10 g of epoxy resin ("EXA-830CRP" manufactured by DIC Corporation) and 3.0 g of compound A were added to a plastic mixing container and mixed using a rotary mixer ("ARE-310" manufactured by Thinky Corporation) to prepare an epoxy resin composition. The "adhesion" was evaluated by the above-mentioned shear adhesion evaluation method (1), the "storage stability at room temperature" was evaluated by the above-mentioned storage stability evaluation method (2), and the "thermal expansion" was evaluated by the above-mentioned thermal expansion evaluation method (3).

[0159] [Example 2] Except that compound A was replaced with compound B, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0160] [Example 3] Except that compound A was replaced with compound C, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0161] [Example 4] Except that compound A was replaced with compound D, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0162] [Example 5] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with compound E. Adhesion, storage stability at room temperature, and thermal expansion were evaluated. Storage stability could not be determined due to the high viscosity of the formulation, and is therefore marked as "-" in the table below.

[0163] [Example 6] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with compound F. Adhesion, storage stability at room temperature, and thermal expansion were evaluated. Storage stability could not be determined due to the high viscosity of the formulation, and is therefore marked as "-" in the table below.

[0164] [Example 7] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with compound G, and the adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0165] [Example 8] Except that compound A was replaced with compound H, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0166] [Example 9] Except that compound A was replaced with compound I, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0167] [Example 10] 10 g of epoxy resin ("EXA-830CRP" manufactured by DIC Corporation) and 0.7 g of silica filler ("SO-E2" manufactured by Admatec Corporation) were mixed using a three-roll mill (BR-150HCV manufactured by AIMEX Corporation). The mixture was then added to a plastic mixing container along with 3.0 g of compound A. The mixture was stirred and mixed using a rotary mixer ("ARE-310" manufactured by Thinky Corporation) to prepare an epoxy resin composition. The "adhesion" was evaluated by the above-mentioned shear adhesion strength evaluation method (1), the "storage stability at room temperature" was evaluated by the above-mentioned storage stability evaluation method (2), and the "thermal expansion" was evaluated by the above-mentioned thermal expansion evaluation method (3).

[0168] [Example 11] Except that the amount of silica filler added was 1.4 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 were evaluated.

[0169] [Example 12] An epoxy resin composition was prepared in the same manner as in Example 10, except that the amount of silica filler added was 13.0 g, and the adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0170] [Example 13] An epoxy resin composition was prepared in the same manner as in Example 1, except that 0.7 g of ethyl propionate was added as a stabilizer. Adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0171] [Example 14] An epoxy resin composition was prepared in the same manner as in Example 1, except that 1.4 g of ethyl propionate was added as a stabilizer. Adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0172] [Example 15] Except for the addition of 0.7 g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0173] [Example 16] Except for the addition of 1.4 g of γ-butyrolactone as a stabilizer, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0174] [Example 17] An epoxy resin composition was prepared in the same manner as in Example 1, except that 1.4 g of ethyl lactate was added as a stabilizer, and the adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0175] [Example 18] An epoxy resin composition was prepared in the same manner as in Example 1, except that 1.4 g of dimethyl succinate was added as a stabilizer. Adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0176] [Example 19] Except that the amount of compound A added was changed to 1.0 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 were evaluated.

[0177] [Example 20] Except that the epoxy resin used was changed 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 were evaluated.

[0178] [Example 21] Except that the epoxy resin used was changed to 5.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Corporation) and 5.0 g of epoxy resin C ("HP4032D" manufactured by DIC 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 were evaluated.

[0179] [Example 22] Except for changing the epoxy resin 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 Karenz 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 were evaluated.

[0180] [Example 23] 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 G ("YX8000" 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 were evaluated.

[0181] [Example 24] 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 H ("YED216D" 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 were evaluated.

[0182] [Example 25] Except for changing the epoxy resin 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 Karenz 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 were evaluated.

[0183] [Example 26] Except for changing the epoxy resin 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 J ("EX-321L" manufactured by Nagase 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 were evaluated.

[0184] [Example 27] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with compound J, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0185] [Example 28] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with compound K, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0186] [Example 29] Compound A was replaced with compound K, and the silica filler was replaced with "SE2200-SEJ" manufactured by Admatec Corporation. The amount of silica filler added was 19.5 g. Otherwise, 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 were evaluated.

[0187] [Example 30] Except that the silica filler was replaced with “SE205-SEJ” manufactured by Admatec, 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 were evaluated.

[0188] [Example 31] Except that the silica filler was replaced with “SE203-SEJ” manufactured by Admatec, 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 were evaluated.

[0189] [Example 32] Except that the silica filler was replaced with “SE1050-SET” manufactured by Admatec, 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 were evaluated.

[0190] [Example 33] Except that the amount of silica filler added was 30.0 g, 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 were evaluated.

[0191] [Example 34] An epoxy resin composition was prepared in the same manner as in Example 24, except that the amount of silica filler added was 39.0 g, and the adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0192] [Example 35] Except that the silica filler used was 31.0 g of "SE2200-SEJ" manufactured by Admatechs and 46.0 g of "FB-5D" manufactured by Denka, 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 were evaluated.

[0193] [Example 36] The silica filler used was 36.0 g of "SE2200-SEJ" manufactured by Admatechs and 57.0 g of "FB-5D" manufactured by Denka. 1.4 g of γ-butyrolactone was added as a stabilizer. Otherwise, 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 were evaluated.

[0194] [Example 37] The epoxy resin used was changed to 6.0 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Corporation) and 4.0 g of epoxy resin H ("YED216D" manufactured by Mitsubishi Chemical Corporation). The silica filler used was 49.0 g of "SE2200-SEJ" manufactured by Admatechs and 81.0 g of "FB-5D" manufactured by Denka. 1.4 g of γ-butyrolactone was added as a stabilizer. Otherwise, the epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature and thermal expansion were evaluated.

[0195] [Example 38] The epoxy resin used was changed to 0.6 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Corporation) and 0.4 g of epoxy resin H ("YED216D" manufactured by Mitsubishi Chemical Corporation). The silica filler used was 27.4 g of magnetic powder of NdFeB alloy with an average particle size of 100 μm. 0.14 g of γ-butyrolactone was added as a stabilizer. Otherwise, the epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0196] [Example 39] The epoxy resin used was changed to 0.6 g of epoxy resin A ("EXA-830CRP" manufactured by DIC Corporation) and 0.4 g of epoxy resin H ("YED216D" manufactured by Mitsubishi Chemical Corporation). The silica filler used was 70.6 g of magnetic powder of NdFeB alloy with an average particle size of 100 μm. 0.14 g of γ-butyrolactone was added as a stabilizer. Otherwise, the epoxy resin composition was prepared in the same manner as in Example 24, and the adhesion, storage stability at room temperature and thermal expansion were evaluated.

[0197] [Example 40] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with compound L, and the adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0198] [Example 41] Except that compound A was replaced with compound M, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0199] [Example 42] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with compound N, and the adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0200] [Example 43] Except that compound A was replaced with compound O, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0201] [Example 44] Except that compound A was replaced with compound P, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0202] [Example 45] Except that compound A was replaced with compound Q, an epoxy resin composition was prepared in the same manner as in Example 1, and its adhesion, storage stability at room temperature, and thermal expansion were evaluated.

[0203] [Example 46] Except that compound A was replaced with 2.25 g of compound A and 0.75 g 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 were evaluated.

[0204] [Example 47] Except that compound A was replaced with 2.0 g of compound B and 1.0 g 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 were evaluated.

[0205] [Example 48] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with 1.0 g of compound B, 1.0 g of compound F and 1.0 g of compound N. Adhesion, storage stability at room temperature and thermal expansion were evaluated.

[0206] [Example 49] Except that compound A was replaced with 2.25 g of compound J and 0.75 g 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 were evaluated.

[0207] [Example 50] Except that compound A was replaced with 2.0 g of compound J and 1.0 g of 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 were evaluated.

[0208] [Example 51] Except that compound A was replaced with 2.25 g of compound K and 0.75 g 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 were evaluated.

[0209] [Example 52] Except that compound A was replaced with 2.5 g of compound L and 0.5 g 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 were evaluated.

[0210] [Example 53] Except that compound A was replaced with 2.0 g of compound L and 1.0 g of 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 were evaluated.

[0211] [Example 54] Except that compound A was replaced with 2.25 g of compound K and 0.75 g of 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 were evaluated.

[0212] [Example 55] Except that compound A was replaced with 2.25 g of compound K and 0.75 g of 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 were evaluated.

[0213] [Example 56] An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was replaced with 0.975 g of compound A, 0.325 g of compound E and 2.6 g of curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane), and the adhesion, storage stability at room temperature and thermal expansion were evaluated.

[0214] [Example 57] Compound A was changed to 0.975 g of compound A, 0.325 g of compound E and 2.6 g of hardener A (4,4'-diamino-3,3'-diethyldiphenylmethane), and the amount of silica filler added was 13.0 g. Otherwise, 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 were evaluated.

[0215] [Example 58] Compound A was replaced with 0.975 g of compound J, 0.325 g of compound M and 2.6 g of hardener A (4,4'-diamino-3,3'-diethyldiphenylmethane), and the amount of silica filler added was 13.0 g. Otherwise, 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 were evaluated.

[0216] [Example 59] Compound A was replaced with 0.975 g of compound K, 0.325 g of compound N and 2.6 g of hardener A (4,4'-diamino-3,3'-diethyldiphenylmethane), and the amount of silica filler added was 13.0 g. Otherwise, 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 were evaluated.

[0217] [Example 60] Compound A was replaced with 0.693 g of compound A, 0.231 g of compound E and 1.8 g of hardener B (a liquid aromatic amine having a diaminodiphenylmethane skeleton), and the amount of silica filler added was 13.0 g. Otherwise, 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 were evaluated.

[0218] [Example 61] Compound A was replaced with 0.693 g of compound J, 0.231 g of compound M and 1.8 g of hardener B (a liquid aromatic amine having a diaminodiphenylmethane skeleton), and the amount of silica filler added was 13.0 g. Otherwise, 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 were evaluated.

[0219] [Example 62] Compound A was replaced with 0.693 g of compound K, 0.231 g of compound N and 1.8 g of hardener B (a liquid aromatic amine having a diaminodiphenylmethane skeleton), and the amount of silica filler added was 13.0 g. Otherwise, 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 were evaluated.

[0220] [Comparative Example 1] Except that compound A was replaced with 3.6 g of hardener 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 were evaluated.

[0221] [Comparative Example 2] Except that compound A was replaced with 2.8 g of curing agent B (a liquid aromatic amine having a diaminodiphenylmethane skeleton), 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 were evaluated.

[0222] [Comparative Example 3] Compound A was replaced with 9.3 g of hardener C ("HN5500" manufactured by Showa Denko Materials Co., Ltd.), and 0.05 g of 2E4MZ (2-ethyl-4-methylimidazolium) was added as a curing accelerator. Otherwise, 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 were evaluated. Hardener C was an acid anhydride with a molecular weight α of 168.

[0223] [Comparative Example 4] Except that compound A was replaced with 0.8 g of hardener 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 were evaluated.

[0224] The composition and evaluation results of each embodiment and comparative example are shown in the following table.

[0225] [Table 1] Composition (parts by weight) of epoxy resin composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Epoxy resin EXA830CRP 10 10 10 10 10 10 10 10 10 10 10 10 jER630 HP4032D jER1032H60 YX4000H CDMDG YX8000 YED216D PETG EX-321L hardener Compound A 3 3 3 3 Compound B 3 Compound C 3 Compound D 3 Compound E 3 Compound F 3 Compound G 3 Compound H 3 Compound I 3 Hardener A Hardener B Hardener C Hardener D hardening accelerator 2E4MZ Inorganic fillers SO-E2 0.7 1.4 13 stabilizer Ethyl propionate γ-Butyrolactone Ethyl lactate dimethyl succinate Molecular weight α of hardener 574 542 603 631 687 797 419 286 659 574 574 574 The α / β value of the hardener 48 54 50 53 57 47 70 57 47 48 48 48 Shear strength (Cu) (adhesion) ◎ ◎ ◎ ◎ ◎ ◎ 〇 〇 〇 ◎ ◎ 〇 Stability after 25℃ for 72 h (storage stability at room temperature) 〇 〇 〇 〇 - - 〇 〇 〇 〇 〇 ◎ TMA CTE (coefficient of thermal expansion) < Tg (ppm / ℃) (thermal thermal expansion) △ △ △ △ △ △ △ △ △ 〇 〇 ◎

[0226] [Table 2] Composition (parts by weight) of epoxy resin composition Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Epoxy resin EXA830CRP 10 10 10 10 10 10 10 jER630 HP4032D jER1032H60 YX4000H CDMDG YX8000 YED216D PETG EX-321L hardener Compound A 3 3 3 3 3 3 1 Compound B Compound C Compound D Compound E Compound F Compound G Compound H Compound I Hardener A Hardener B Hardener C Hardener D hardening accelerator 2E4MZ Inorganic fillers SO-E2 stabilizer Ethyl propionate 0.7 1.4 γ-Butyrolactone 0.7 1.4 Ethyl lactate 1.4 dimethyl succinate 1.4 Molecular weight α of hardener 574 574 574 574 574 574 574 The α / β value of the hardener 48 48 48 48 48 48 48 Shear strength (Cu) (adhesion) ◎ ◎ ◎ ◎ ◎ ◎ ◎ Stability after 25℃ for 72 h (storage stability at room temperature) ◎ ◎ ◎ ◎ ◎ ◎ ◎ TMA CTE < Tg (ppm / ℃) (thermal expansion) △ △ △ △ △ △ △

[0227] [Table 3] Composition (parts by weight) of epoxy resin composition Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Epoxy resin EXA830CRP 5 5 4 4 4 4 4 jER630 5 4 4 4 4 4 HP4032D 5 jER1032H60 1 1 1 YX4000H 1 1 CDMDG 1 YX8000 1 YED216D 1 PETG 1 EX-321L 1 hardener Compound A 3 3 3 3 3 3 3 Compound B Compound C Compound D Compound E Compound F Compound G Compound H Compound I Hardener A Hardener B Hardener C Hardener D hardening accelerator 2E4MZ Inorganic fillers SO-E2 stabilizer Ethyl propionate γ-Butyrolactone Ethyl lactate dimethyl succinate Molecular weight α of hardener 574 574 574 574 574 574 574 The α / β value of the hardener 48 48 48 48 48 48 48 Shear strength (Cu) (adhesion) ◎ ◎ ◎ ◎ ◎ ◎ ◎ Stability after 25℃ for 72 h (storage stability at room temperature) 〇 〇 〇 〇 〇 〇 〇 TMA CTE < Tg (ppm / ℃) (thermal expansion) △ △ △ △ △ △ △

[0228] [Table 4] Composition (parts by weight) of epoxy resin composition Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Epoxy resin EXA830CRP 10 10 10 10 10 10 10 10 10 YED216 hardener Compound A Compound B Compound C Compound D Compound E Compound F Compound G Compound H Compound I Compound J 3 compound K 3 3 3 3 3 3 3 3 Compound L Compound M Compound N Compound O Compound P Compound Q Hardener A Hardener B Hardener C Hardener D hardening accelerator 2E4MZ Inorganic fillers SO-E2 SE2200-SEJ 19.5 30 39 31 SE205-SEJ 19.5 SE203-SEJ 19.5 SE1050-SET 19.5 FB-5D 46 NdFeB powder stabilizer Ethyl propionate γ-Butyrolactone Ethyl lactate dimethyl succinate Molecular weight α of hardener 839 811 811 811 811 811 811 811 811 The α / β value of the hardener 47 45 45 45 45 45 45 45 45 Shear strength (Cu) (adhesion) ◎ ◎ 〇 〇 〇 〇 〇 〇 〇 Stability after 25℃ for 72 h 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ TMA CTE < Tg (ppm / ℃) (thermal expansion) △ △ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[0229] [Table 5] Composition (parts by weight) of epoxy resin composition Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 Epoxy resin EXA830CRP 10 6 0.6 0.6 10 10 10 10 10 YED216 4 0.4 0.4 hardener Compound A Compound B Compound C Compound D Compound E Compound F Compound G Compound H Compound I Compound J compound K 3 3 0.3 0.3 Compound L 3 Compound M 3 Compound N 3 Compound O 3 Compound P 3 Compound Q Hardener A Hardener B Hardener C Hardener D hardening accelerator 2E4MZ Inorganic fillers SO-E2 SE2200-SEJ 36 49 SE205-SEJ SE203-SEJ SE1050-SET FB-5D 57 81 NdFeB powder 27.4 70.6 stabilizer Ethyl propionate γ-Butyrolactone 1.4 1.4 0.14 0.14 Ethyl lactate dimethyl succinate Molecular weight α of hardener 811 811 811 811 591 653 625 613 585 The α / β value of the hardener 45 45 45 45 45 65 63 61 59 Shear strength (Cu) (adhesion) 〇 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ Stability after 25℃ for 72 h ◎ ◎ ◎ ◎ 〇 〇 〇 〇 〇 TMA CTE < Tg (ppm / ℃) (thermal expansion) ◎ ◎ ◎ ◎ △ △ △ △ △

[0230] [Table 6] Composition (parts by weight) of epoxy resin composition Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 Example 52 Example 53 Epoxy resin EXA830CRP 10 10 10 10 10 10 10 10 10 YED216 hardener Compound A 2.25 Compound B 2 1 Compound C Compound D Compound E 0.75 1 Compound F 1 Compound G Compound H Compound I Compound J 2.25 2 compound K 2.25 Compound L 2.5 2 Compound M 0.75 Compound N 1 0.75 0.5 Compound O Compound P Compound Q 3 1 1 Hardener A Hardener B Hardener C Hardener D hardening accelerator 2E4MZ Inorganic fillers SO-E2 SE2200-SEJ SE205-SEJ SE203-SEJ SE1050-SET FB-5D NdFeB powder stabilizer Ethyl propionate γ-Butyrolactone Ethyl lactate dimethyl succinate Molecular weight α of hardener 320 574 / 687 542 / 687 542 / 797 / 625 839 / 653 839 / 320 811 / 625 591 / 625 591 / 320 The α / β value of the hardener 64 48 / 57 54 / 57 54 / 47 / 63 47 / 65 47 / 64 45 / 63 45 / 63 45 / 64 Shear strength (Cu) (adhesion) 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Stability after 25℃ for 72 h 〇 〇 〇 〇 〇 〇 〇 〇 〇 TMA CTE < Tg (ppm / ℃) (thermal expansion) △ △ △ △ △ △ △ △ △

[0231] [Table 7] Composition (parts by weight) of epoxy resin composition Example 54 Example 55 Example 56 Example 57 Example 58 Example 59 Example 60 Example 61 Example 62 Epoxy resin EXA830CRP 10 10 10 10 10 10 10 10 10 YED216 hardener Compound A 0.975 0.975 0.693 Compound B Compound C Compound D Compound E 0.325 0.325 0.231 Compound F Compound G Compound H Compound I Compound J 0.975 0.693 compound K 2.25 2.25 0.975 0.693 Compound L Compound M 0.325 0.231 Compound N 0.325 0.231 Compound O Compound P 0.75 Compound Q 0.75 Hardener A 2.6 2.6 2.6 2.6 Hardener B 1.8 1.8 1.8 Hardener C Hardener D hardening accelerator 2E4MZ Inorganic fillers SO-E2 13 13 13 13 13 13 SE2200-SEJ SE205-SEJ SE203-SEJ SE1050-SET FB-5D NdFeB powder stabilizer Ethyl propionate γ-Butyrolactone Ethyl lactate dimethyl succinate Molecular weight α of hardener 811 / 585 811 / 320 574 / 687 574 / 687 839 / 653 811 / 625 574 / 687 839 / 653 811 / 625 The α / β value of the hardener 45 / 59 45 / 64 48 / 57 48 / 57 47 / 65 45 / 63 48 / 57 47 / 65 45 / 63 Shear strength (Cu) (adhesion) ◎ ◎ ◎ 〇 〇 〇 〇 〇 〇 Stability after 25℃ for 72 h 〇 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ TMA CTE < Tg (ppm / ℃) (thermal expansion) △ △ △ ◎ ◎ ◎ ◎ ◎ ◎

[0232] [Table 8] Composition (parts by weight) of epoxy resin composition Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Epoxy resin EXA830CRP 10 10 10 10 YED216 hardener Compound A Compound B Compound C Compound D Compound E Compound F Compound G Compound H Compound I Compound J compound K Compound L Compound M Compound N Compound O Compound P Compound Q Hardener A 3.6 Hardener B 2.8 Hardener C 9.3 Hardener D 0.8 hardening accelerator 2E4MZ 0.05 Inorganic fillers SO-E2 SE2200-SEJ SE205-SEJ SE203-SEJ SE1050-SET FB-5D NdFeB powder stabilizer Ethyl propionate γ-Butyrolactone Ethyl lactate dimethyl succinate Molecular weight α of hardener 226 178 168 84 The α / β value of the hardener 113 89 56 twenty one Shear strength (Cu) (adhesion) △ △ × × Stability after 25℃ for 72 h × × ◎ 〇 TMA CTE < Tg (ppm / ℃) (thermal expansion) △ 〇 △ ×

[0233] The results in each table confirm that the epoxy resin composition using a curing agent with a specific molecular weight (molecular weight α) and molecular structure (α / β ratio) exhibits excellent adhesion. Furthermore, the results in each table confirm that the epoxy resin composition using an amine imine compound with a specific molecular weight and molecular structure as the curing agent in this embodiment exhibits good storage stability. On the other hand, it is confirmed that when a compound with a molecular weight or molecular structure outside the scope of the patent application is used as the curing agent, the storage stability or adhesion is poor. Specifically, it is confirmed that the liquid aromatic amine used in Comparative Examples 1 and 2 or the acid anhydride used in Comparative Example 3 each have poor adhesion, and consequently, the storage stability is also poor in Comparative Examples 1 and 2. Also, the results in Comparative Example 4 show that when the curing agent ratio α / β is less than 30, the adhesion and thermal expansion are poor. The results in Examples 10 and 11 confirm that excellent low thermal expansion is exhibited by adding an inorganic filler. Furthermore, the results of Examples 12-17 confirm that the storage stability is further improved by adding a stabilizer with a specific structure.

[0234] This case is based on Japanese Patent Application No. 2021-213746, filed with the Japan Patent Office on December 28, 2021, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0235] The epoxy resin composition of the present invention is industrially applicable as a sealing material, adhesive, printed substrate, coating, composite material, underfill or molding compound or other semiconductor sealing material, conductive adhesive such as ACF, solder resist or cover film or other printed wiring substrate, prepreg or other composite material impregnated with glass fiber or carbon fiber or other materials.

Claims

1. An epoxy resin composition comprising (A) an epoxy resin and (B) a heteroatom-containing curing agent, wherein the molecular weight α of the heteroatom-containing curing agent (B) is 200 ≤ α ≤ 1200, the ratio α / β of the molecular weight α to the number of heteroatoms β in the structure of the heteroatom-containing curing agent (B) is 30 ≤ α / β ≤ 95, and the heteroatom-containing curing agent (B) comprises an aminoimine compound represented by formula (1), formula (2) or formula (3) below. [Chemical 1] In formulas (1) and (2), R1 independently represents a hydrogen atom, or an organogroup with 1 to 15 carbon atoms that may have a hydroxyl, ester, or ether bond, and is monovalent or n-valent; R2 and R3 independently represent an alkyl, aryl, aralkyl group with 1 to 12 carbon atoms that is unsubstituted or substituted, or an acridine ring, pyrrole ring, α-porphyrin ring, thiazoline ring, piperidine ring, hexamethyleneimine ring, or nitropyridine ring formed by the linkage of R2 and R3; R4 independently represents a hydrogen atom, or an organogroup that may contain an oxygen atom. A monovalent or n-valent organic group; n represents an integer from 1 to 3; in formula (3), R1 represents a hydrogen atom, or a monovalent or n-valent organic group having 1 to 15 carbon atoms that may have hydroxyl, carbonyl, ester or ether bonds; R2 and R3 independently represent alkyl, aryl, aralkyl, or heterocycles having 1 to 12 carbon atoms that are unsubstituted or substituted, or having 7 or fewer carbon atoms formed by the linkage of R2 and R3; R4 represents a hydrogen atom, or a monovalent or n-valent organic group that may contain an oxygen atom; n is 2 or 3).

2. The epoxy resin composition of claim 1, wherein n in formula (2) above is 2 or 3.

3. The epoxy resin composition of claim 1, further comprising (C) an inorganic filler.

4. The epoxy resin composition of claim 3, wherein the content of the inorganic filler (C) is more than 5% by mass and less than 98% by mass relative to the total epoxy resin composition.

5. The epoxy resin composition of claim 1, further comprising (D) a stabilizer.

6. The epoxy resin composition of claim 5, wherein the stabilizer (D) above comprises a compound represented by formula (A) or (B) below, [Chemical 2] (in formula (A), R5 and R6 independently represent a hydrogen atom, or an organic group having a carbon number of 1 to 15 or an n-valent group having a hydroxyl, carbonyl, ester or ether bond, where n represents an integer of 2 to 3) [Chemical 3] (in formula (B), R7 represents an organic group having a carbon number of 1 to 15 or an n-valent group having a hydroxyl, carbonyl, ester or ether bond, where n represents an integer of 2 to 3).

7. The epoxy resin composition of claim 5, wherein the content of the stabilizer of claim (D) is more than 1 part by mass and less than 30 parts by mass relative to 100 parts by mass of epoxy resin of claim (A).

8. A cured compound, which is a cured compound of the epoxy resin composition of any one of claims 1 to 7.

9. A sealing material comprising the hardened material as claimed in claim 8.

10. The sealing material in claim 9 is a sealing material for semiconductors.

11. An adhesive comprising an epoxy resin composition as claimed in any one of claims 1 to 7.