Epoxy resin composition, cured product, encapsulant, adhesive, and semiconductor package and method for manufacturing the same.

Abstract

The present invention aims to provide epoxy resin compositions, cured products, encapsulants, adhesives, semiconductor packages, and methods for manufacturing the same, which exhibit excellent penetration and heat dissipation performance in narrow gaps and large areas of electronic components. [Solution] An epoxy resin composition comprising (A) epoxy resin, (B) curing agent, and (C) inorganic filler, wherein (C) inorganic filler is other than silica, and (B) curing agent contains a compound represented by a specific formula (1), formula (2), or formula (3).

Description

Technical Field

[0001] The present invention relates to an epoxy resin composition, a cured product, a sealing material, an adhesive, and a semiconductor package and a method for manufacturing the same.

Background Art

[0002] Epoxy resins are used in a wide range of applications such as paints, electrical and electronic insulation materials, and adhesives because their cured products have various performances.

[0003] For example, Patent Document 1 describes an epoxy resin composition using 2-ethyl-4-methylimidazole as a curing accelerator and an alumina filler as an inorganic filler.

[0004] Also, for example, Patent Document 2 describes an epoxy resin composition containing silica particles as a filler.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] Currently, as a commonly used epoxy resin composition, there is a so-called two-component epoxy resin composition in which an epoxy resin and a curing agent are mixed during use.

[0007] While two-component epoxy resin compositions can cure at room temperature, they require separate storage of the epoxy resin and curing agent, followed by weighing and mixing as needed before use. This makes storage and handling cumbersome. Furthermore, the limited usable time prevents pre-mixing large quantities, leading to frequent mixing and inevitably reducing efficiency.

[0008] To address the challenges of these two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed. For example, epoxy resin compositions in which a curing agent for epoxy resins is blended with the epoxy resin can be considered.

[0009] Incidentally, the demands on electronic devices and equipment these days are diverse. Such demands include, for example, miniaturization, increased functionality, weight reduction, and multi-functionality. More specifically, for example, in semiconductor chip mounting technology, there is a demand for further miniaturization, miniaturization, and high density through the reduction of electrode pad and pad pitch.

[0010] Furthermore, underfill is used as an adhesive placed in the gap between the chip and the substrate for purposes such as protecting the bump connection area and the circuit surface of the chip. From the perspective of meeting the demands for highly fine pitch, there is a need for underfill that can penetrate into even narrower gaps.

[0011] Furthermore, in recent years, there has been a growing demand not only for finer pitch but also for larger semiconductor chip areas, which may increase the penetration time of the underfill. Therefore, underfills must exhibit minimal viscosity changes in high-temperature environments during penetration and during storage. Furthermore, as electronic devices become smaller, more compact, and denser, large amounts of electrical energy are injected into smaller areas, leading to rapid heat generation that can cause performance degradation and deterioration. Therefore, high heat dissipation capabilities are also required.

[0012] As described above, latent curing agents constituting one-component epoxy resin compositions are required to exhibit both good curing properties after mixing with the epoxy resin and excellent storage stability. Furthermore, good penetration into fine areas such as between densely packed fibers like carbon fibers and glass fibers, and in narrow gap areas of electronic components, as well as good heat dissipation performance, are also required.

[0013] The epoxy resin composition described in Patent Document 1 above uses imidazole as a curing accelerator, and has issues with viscosity stability at high temperatures, so there is room for improvement in penetration into narrow gaps and large areas of electronic components.

[0014] The epoxy resin composition described in Patent Document 2 above uses a high content of silica particles, which have low thermal conductivity, as a filler, and therefore there is room for improvement in its heat dissipation performance.

[0015] The problem that the present invention aims to solve is, for example, to provide epoxy resin compositions, cured products, encapsulants, adhesives, semiconductor packages, and methods for manufacturing the same, which have excellent penetration and heat dissipation performance in narrow gaps and large areas of electronic components. [Means for solving the problem]

[0016] The present invention includes the following embodiments. [1] (A) epoxy resin, (B) curing agent, and (C) inorganic filler are included. The inorganic filler (C) mentioned above is other than silica. An epoxy resin composition wherein the curing agent (B) contains a compound represented by the following formula (1), formula (2), or formula (3). [ka] (In formulas (1) to (3), each R1 independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms, which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or they are linked to form a heterocyclic ring having 7 or fewer carbon atoms; R4 each independently represents a hydrogen atom or an n-valent organic group having 1 to 60 carbon atoms, which may contain an oxygen atom; n represents an integer of 1 to 3. R5 represents a nitrogen atom having a negative charge, and R6 represents a nitrogen atom having a positive charge.) [2] The epoxy resin composition according to [1], wherein the (C) inorganic filler is one or more selected from the group consisting of alumina, aluminum nitride, boron nitride, and silicon carbide. [3] The epoxy resin composition according to [1], wherein the (C) inorganic filler is alumina. [4] The epoxy resin composition according to [1], wherein the (C) inorganic filler contains one or more selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide and alumina. [5] The epoxy resin composition according to any one of [1] to [4], wherein the content of the (C) inorganic filler is 68.5% by mass or more and 90% by mass or less. [6] The epoxy resin composition according to any one of [1] to [5], further containing (D) silica. [7] The epoxy resin composition according to [6], wherein the mass ratio of the (C) inorganic filler to the (D) silica ((C) inorganic filler: (D) silica) is 99:1 to 80:20. [8] The epoxy resin composition according to any one of [1] to [7], wherein the average particle size of the (C) inorganic filler is 0.01 μm or more and 5 μm or less. [9] The epoxy resin composition according to any one of [1] to [8], wherein the maximum particle size of the (C) inorganic filler is 10 μm or less.

[10] The epoxy resin composition according to [6], comprising silica with a particle size of 100 nm or less as (D) silica.

[11] The epoxy resin composition according to any one of [1] to

[10] , wherein the epoxy resin (A) comprises a p-aminophenol type epoxy resin.

[12] The epoxy resin composition according to any one of [1] to

[11] , comprising an epoxy resin having a solubility parameter (SP value) of 15 or more and 21 or less as the (A) epoxy resin.

[13] An epoxy resin composition according to any one of [1] to

[12] , wherein the viscosity at 100°C is 1.4 Pa·s or less.

[14] The epoxy resin composition according to any one of [1] to

[13] , wherein the viscosity increase rate after being left at 100°C for 60 minutes is 1 to 40 times.

[15] An epoxy resin composition according to any one of [1] to

[14] , wherein the reaction rate when cured at 165°C is 85% or more and 100% or less.

[16] A cured product of an epoxy resin composition described in any of [1] to

[15] .

[17] A sealing material comprising the cured product described in

[16] .

[18] The encapsulating material described in

[17] , which is an encapsulating material for semiconductors.

[19] An adhesive comprising an epoxy resin composition as described in any of [1] to

[15] .

[20] A semiconductor package containing the cured product described in

[16] . [twenty one] A method for manufacturing a semiconductor package, comprising the step of manufacturing a semiconductor package using an epoxy resin composition described in any of [1] to

[15] . [Effects of the Invention]

[0017] According to the present invention, for example, it is possible to provide epoxy resin compositions, cured products, encapsulants, adhesives, semiconductor packages, and methods for manufacturing the same that are excellent in terms of penetration and heat dissipation performance in narrow gaps and large areas of electronic components. [Modes for carrying out the invention]

[0018] The embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail below.

[0019] The following embodiments are illustrative for explaining the present invention and are not intended to limit the present invention to the following. The present invention can be implemented with appropriate modifications without departing from its spirit. In this specification, when "~" is used to enclose numerical values ​​or physical properties, it is used to include the values ​​before and after it.

[0020] In numerical ranges described stepwise within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that range may be replaced with the values ​​shown in the examples.

[0021] In this specification, when groups (atomic groups) are not explicitly labeled as substituted or unsubstituted, the term includes both substituted and unsubstituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups.

[0022] Epoxy resin compositions The epoxy resin composition of this embodiment contains (A) epoxy resin, (B) curing agent, and (C) inorganic filler, wherein (C) inorganic filler is other than silica, and (B) curing agent contains a compound represented by the following formula (1), formula (2), or formula (3). [ka] (In formulas (1) to (3), R1 independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms, which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 independently represent an unsubstituted or substituted alkyl, aryl, or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle with 7 or fewer carbon atoms; R4 independently represents a hydrogen atom or an n-valent organic group having 1 to 60 carbon atoms, which may contain an oxygen atom; n represents an integer from 1 to 3. R5 represents a negatively charged nitrogen atom, and R6 represents a positively charged nitrogen atom.)

[0023] ((A) Epoxy resin) The epoxy resin composition of this embodiment contains (A) epoxy resin. (A) The epoxy resin is not particularly limited, 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, phenylbenzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcinol type epoxy resin, methylresorcinol type epoxy resin, catechol type epoxy resin, N,N-diglycidylaniline type epoxy resin, ethylene oxide-added bisphenol A type epoxy resin, propylene oxide-added bisphenol Examples include bifunctional epoxy resins such as phenol A type epoxy resin, ethylene oxide-added bisphenol F type epoxy resin, p-aminophenol type epoxy resin, and propylene oxide-added bisphenol F type epoxy resin; trifunctional epoxy resins such as trisphenol type epoxy resin, N,N-diglycidylaminobenzene type epoxy resin, o-(N,N-diglycidylamino)toluene type epoxy resin, triazine type epoxy resin, ethylene oxide-added trisphenol type epoxy resin, and propylene oxide-added trisphenol type epoxy resin; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resin and diaminobenzene type epoxy resin; polyfunctional epoxy resins such as pentaerythritol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphthol aralkyl type epoxy resin, and brominated phenol novolac type epoxy resin; and alicyclic epoxy resins.

[0024] (A) As the epoxy resin, a single bisphenol F type epoxy resin, a combination of a bisphenol F type epoxy resin and a bisphenol A type epoxy resin, a combination of a bisphenol F type epoxy resin and a naphthalene type epoxy resin, etc., can be used. From the viewpoint of achieving both permeability and reliability, it is preferable that (A) the epoxy resin contains a p-aminophenol type epoxy resin. These can be used individually or in combination of two or more. Furthermore, epoxy resins modified with isocyanates or the like can also be used in combination.

[0025] The epoxy resin composition of this embodiment may further contain an epoxy-based reactive diluent. The epoxy-based reactive diluents mentioned above are not particularly limited, but examples include n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6 Examples include hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, vinylcyclohexene dioxide, Mitsubishi Chemical Corporation's product name: YX-8000, Sakamoto Pharmaceutical Co., Ltd.'s product name: SR-8EGS, hexahydrophthalate diglycidyl ether, resorcinol diglycidyl ether, tert-butylhydroquinone diglycidyl ether, polyoxyalkylene bisphenol A diglycidyl ether, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, and N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline.

[0026] (A) The epoxy resin content is not particularly limited, but the lower limit of the content is preferably 7% by mass or more, more preferably 8% by mass or more, and even more preferably 8.5% by mass or more, relative to the total mass of the epoxy resin composition. The upper limit of the epoxy resin content is preferably 15% by mass or less, more preferably 14% by mass or less, and even more preferably 13% by mass or less. By setting the epoxy resin content within the above range, high fluidity tends to be obtained.

[0027] The epoxy resin composition of this embodiment more preferably contains an epoxy resin having a solubility parameter (SP value) of 15 or more and 21 or less, among the epoxy resins described above. By including such epoxy resins, epoxy resin compositions with excellent injection properties and no clogging tend to be obtained. (SP value) In this specification, the solubility parameter (SP value) refers to the Hansen solubility parameter, which can be determined using the Hansen solubility sphere method and can be determined using the HSP calculation software HSPiP.

[0028] The SP value can also be expressed by dividing it into three components as follows: dispersion force term: energy due to intermolecular dispersion forces (δD), polarity term: energy due to intermolecular dipole interactions (δP), and hydrogen bond term: energy due to intermolecular hydrogen bonds (δH). (SP value) 2 =(δD) 2 +(δP) 2 +(δH) 2 The epoxy resins mentioned above are not particularly limited, but examples include 1,6-hexanediol diglycidyl ether (SP value: 19.39, δD: 16.90, δP: 7.60, δH: 5.70), 2-ethylhexylglycidyl ether (SP value: 17.36, δD: 16.20, δP: 4.60, δH: 4.20), hydrogenated bisphenol a type epoxy resin (YX8000D, SP value: 18.76, δD: 17.40, δP: 5.70, δH: 4.10), and butyl glycidyl ether (DY-BP) SP value 18.31, δD: 16.40, δP: 6.00, δH: 5.50. In the epoxy resin (A) used in the epoxy resin composition of this embodiment, the preferred ranges for each component are as follows: The SP value is preferably 15 or higher, more preferably 15.5 or higher, even more preferably 20 or lower, and even more preferably 19.5 or lower. δD is preferably 13 or higher, more preferably 14 or higher, even more preferably 18 or lower, and even more preferably 18 or lower. δP is preferably 1 or higher, more preferably 2 or higher, even more preferably 8 or lower, and even more preferably 7.6 or lower. δH is preferably 1 or higher, more preferably 2 or higher, even more preferably 7 or lower, and even more preferably 6 or lower.

[0029] ((B) Hardener) The epoxy resin composition of this embodiment contains (B) a curing agent. The curing agent (B) used in this embodiment contains at least one compound (hereinafter also referred to as "compound B") selected from the group consisting of the compound represented by the following formula (1), the compound represented by the following formula (2), and the compound represented by the following formula (3).

[0030] [ka] (In formulas (1) to (3), R1 independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms, which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R2 and R3 independently represent an unsubstituted or substituted alkyl, aryl, or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle with 7 or fewer carbon atoms; R4 independently represents a hydrogen atom or an n-valent organic group having 1 to 60 carbon atoms, which may contain an oxygen atom; n represents an integer from 1 to 3. R5 represents a negatively charged nitrogen atom, and R6 represents a positively charged nitrogen atom.)

[0031] In equations (1), (2), and (3), R1 is presumed to contribute to the reduction of energy in the cleavage of the NN bond. R2 and R3 are presumed to contribute to the reduction of energy in the cleavage reaction due to steric hindrance and resulting in destabilization. R4 is presumed to contribute to the suppression of liquefaction of the compound and the decrease in the glass transition temperature of the resulting cured product. The details of each unit are described below.

[0032] In formulas (1), (2), and (3), R1 independently represents either a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms, which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond.

[0033] In R1, there are no particular limitations on the organic group, but examples include a hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted by a hydroxyl group or a carbonyl group, or a group in which some of the carbon atoms in a hydrocarbon group are replaced by an ester bond or an ether bond.

[0034] In R1, the hydrocarbon group is not particularly limited, but examples include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octinyl, desynyl, dodecynyl, hexadecynyl, and octadecynyl groups; aryl groups such as phenyl groups; and aralkyl groups including combinations of alkyl groups and phenyl groups such as methylphenyl, ethylphenyl, and propylphenyl groups. In R1, the divalent hydrocarbon group is not particularly limited, but examples include methylene group, ethylene group, propylene group, 2,2-dimethylpropylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, undecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, neopentylene group, dimethylbutylene group, methylhexylene group, and ethyl Examples of linear or branched alkylene groups include hexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene. Among these, R1 can be a methylene group, an ethylene group, or a propylene group.

[0035] In R1, the organic group may have other substituents. Substituents are not particularly limited, but examples include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azi groups, thiol groups, sulfo groups, nitro groups, hydroxyl groups, acyl groups, and aldehyde groups. In R1, the number of carbon atoms in the organic group is 1 to 15, preferably 1 to 12, and more preferably 1 to 7. Having the number of carbon atoms in the organic group within this range makes it easier to obtain a liquid compound with appropriate viscosity, and tends to improve the curing performance of the compound. Furthermore, having the number of carbon atoms in the organic group within this range improves the availability of raw materials.

[0036] R2 and R3 each independently represent an unsubstituted or substituted alkyl, aryl, or aralkyl group having 1 to 12 carbon atoms, or they can be linked to form a heterocycle having 7 or fewer carbon atoms.

[0037] In R2 and R3, the alkyl group having 1 to 12 carbon atoms is not particularly limited, but examples include linear alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl groups; branched alkyl groups such as isopropyl, isobutyl, t-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl groups. Furthermore, the alkyl group may include a combination of a linear alkyl group or a branched alkyl group and a cyclic alkyl group. In addition, the alkyl group may contain an unsaturated bonding group.

[0038] In R2 and R3, the number of carbon atoms in the alkyl group is independently 1 to 12, preferably 2 to 10, and more preferably 5 to 10. Having two or more carbon atoms in the alkyl groups of R2 and R3 tends to avoid the use of raw materials that pose risks such as explosion or toxicity. Furthermore, by setting the number of carbon atoms in the alkyl groups in R2 and R3 to 5 or more, it becomes easier to obtain a liquid compound with appropriate viscosity, and the curing performance of the compound tends to improve.

[0039] The aryl groups in R2 and R3 are not particularly limited, but examples include phenyl groups and naphthyl groups.

[0040] In R2 and R3, the aralkyl group is not particularly limited, but examples include a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.

[0041] Among these, aralkyl groups are preferred for R2 and R3, and methylphenyl groups (benzyl groups) are more preferred. This tends to further improve the curing performance of the compound. The number of carbon atoms in the aryl group and aralkyl group represented by R2 or R3 is not particularly limited, but for example, it is 6 to 20.

[0042] The substituents of alkyl, aryl, or aralkyl groups in R2 and R3 are not particularly limited, but examples include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azi groups, thiol groups, sulfo groups, nitro groups, hydroxyl groups, acyl groups, aldehyde groups, and the like.

[0043] R2 and R3 may be linked together to form a heterocycle with 7 or fewer carbon atoms. There are no particular restrictions on the heterocycle, but examples include four-membered rings such as azetidine rings; five-membered rings such as pyrrolidine rings, pyrrole rings, morpholine rings, and thiadin rings; six-membered rings such as piperidine rings; and seven-membered rings such as hexamethyleneimine rings and azepine rings. Among these, pyrrole rings, morpholine rings, thiadin rings, piperidine rings, hexamethyleneimine rings, and azepine rings are preferred as heterocycles, with 6-membered and 7-membered rings being more preferred. Having such groups makes it easier to obtain liquid compounds and tends to improve the curing performance of the compounds.

[0044] Furthermore, the substituents in the heterocycle are not particularly limited, but examples include alkyl groups, aryl groups, or substituents at R2 and R3 as described above. In addition, when the heterocycle has an alkyl group as a substituent, an example is a methyl group bonded to a carbon atom adjacent to R6.

[0045] In formulas (1), (2), and (3), R4 independently represents either a hydrogen atom or an n-valent organic group having 1 to 60 carbon atoms, which may contain an oxygen atom. In R4, there are no particular limitations on the organic group, but examples include hydrocarbon groups, groups in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is replaced by a hydroxyl group, a carbonyl group, or a group containing a silicon atom, and groups in which some of the carbon atoms in a hydrocarbon group are replaced by an ester bond, an ether bond, or a silicon atom. In R4, the hydrocarbon group is not particularly limited, but examples include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octinyl, desynyl, dodecynyl, hexadecynyl, and octadecynyl groups; aryl groups such as phenyl groups; and aralkyl groups including combinations of alkyl groups and phenyl groups such as methylphenyl, ethylphenyl, and propylphenyl groups. In R4, the divalent hydrocarbon group is not particularly limited, but examples include methylene group, ethylene group, propylene group, 2,2-dimethylpropylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, undecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, neopentylene group, dimethylbutylene group, methylhexylene group, and ethyl Examples of linear or branched alkylene groups include hexylene, dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene.

[0046] In R4, the hydrocarbon group is not particularly limited, but may include 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. The organic group containing the bisphenol skeleton is not particularly limited, but examples include groups in which a polyoxyalkylene group is added to the hydroxyl group of each bisphenol skeleton.

[0047] Among these, the organic group represented by R4 in formula (1) or formula (2) is preferably an alkyl group, an alkenyl group, or an aralkyl group, more preferably an alkyl group and an alkenyl group, and even more preferably a branched alkyl group and a branched alkenyl group. These preferred groups may have substituents. Having such groups makes it easier to obtain a liquid compound with appropriate viscosity, and tends to improve the curing performance of the compound. In addition, the glass transition temperature (Tg) of the cured product obtained using the compound tends to improve.

[0048] In R4, the number of carbon atoms in the organic group is 1 to 60, preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 15, and even more preferably 1 to 8. Having the number of carbon atoms in the organic group in R4 within this range makes it easier to obtain a liquid compound with appropriate viscosity, and tends to improve the curing performance of the compound. Furthermore, the Tg of the cured product obtained using this compound is improved, and the availability of raw materials is further enhanced due to the number of carbon atoms in the organic group in R4 being within this range.

[0049] Among the above, R4 in formula (1) or formula (2) is preferably a linear or branched alkyl group having 3 to 12 carbon atoms, or a linear or branched alkenyl group having 3 to 6 carbon atoms. Having such a group makes it easier to obtain a liquid compound with appropriate viscosity, and tends to further improve the curing performance of the compound. From the viewpoint of controlling the curing temperature or viscosity, (B) the curing agent preferably contains multiple compounds represented by formula (1), formula (2), or formula (3). It is also possible to include multiple compounds with different structures represented by the same formula.

[0050] Particularly from the viewpoint of viscosity control, it is preferable that the curing agent (B) contains the compound represented by formula (1) and the compound represented by formula (3). When the mixture contains multiple compounds represented by formula (1), formula (2), or formula (3), it is preferable that the content of the compound represented by formula (1) is between 0.1% by mass and 99.5% by mass relative to the total amount of compounds represented by formulas (1) to (3). This allows for easy control of viscosity. A composition containing multiple compounds represented by formula (1), formula (2), or formula (3) can be obtained by mixing multiple compounds, or by simultaneously producing multiple compounds in the compound production method described later.

[0051] The compounds represented by formula (1), formula (2), or formula (3) can be produced by reacting, for example, ester compounds, hydrazine compounds, and glycidyl ether compounds.

[0052] The ester compounds are not particularly limited, but examples include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds.

[0053] Specific examples of monocarboxylic acid ester compounds are not limited to methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, isovalerate, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotate, methyl isocrotonate, methyl benzoylmate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl, and the like. Alternatively, ethyl esters, propyl esters, etc., may be used instead.

[0054] Specific examples of dicarboxylic acid ester compounds are not limited to those mentioned above, but include, for example, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimerate, dimethyl suberate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate. Alternatively, cyclic esters may be used instead. Specific examples of cyclic esters are not limited to α-acetolactone, β-propionactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone. Alternatively, diethyl esters, dipropyl esters, etc., may be used.

[0055] Among these, from the viewpoint of curability and liquefaction, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl acrylate, methyl methacrylate, methyl crotate, methyl isocrotonate, methyl benzoylmate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, γ-butyrolactone, δ-valerolactone, and γ-valerolactone are preferred as ester compounds.

[0056] The hydrazine compounds are not particularly limited, but examples include dimethylhydrazine, diethylhydrazine, methylethylhydrazine, methylpropylhydrazine, methylbutylhydrazine, methylpentylhydrazine, methylhexylhydrazine, ethylpropylhydrazine, ethylbutylhydrazine, ethylpentylhydrazine, ethylhexylhydrazine, dipropylhydrazine, dibutylhydrazine, dipentylhydrazine, dihexylhydrazine, methylphenylhydrazine, ethylphenylhydrazine, methyltolylhydrazine, ethyltolylhydrazine, diphenylhydrazine, benzylphenylhydrazine, dibenzylhydrazine, dinitrophenylhydrazine, 1-aminopiperidine, N-aminohomopiperidine, 1-amino-2,6-dimethylpiperidine, 1-aminopyrrolidine, 1-amino-2-methylpyrrolidine, 1-amino-2-phenylpyrrolidine, and 1-aminomorpholine. Among these, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred as hydrazine compounds from the viewpoint of curability and liquefaction. Furthermore, among these, dibenzylhydrazine and 1-aminopiperidine are more preferred from the viewpoint of availability and safety. The hydrazine compound may be used alone or in combination of two or more.

[0057] The glycidyl ether compound is not particularly limited, but for example, monofunctional monoglycidyl ether compounds, bifunctional or polyglycidyl ether compounds, etc., can be used.

[0058] Specific examples of monoglycidyl ether compounds are not limited to methyl glycidyl ether, but include, for example, methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, orthophenylphenol glycidyl ether, benzyl glycidyl ether, biphenylyl glycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, and 3-[diethoxy(methyl)silyl]propyl glycidyl ether.

[0059] Specific examples of polyglycidyl ether compounds are not limited to, but include, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, Examples include aliphatic polyglycidyl ethers such as glycerin polyglycidyl ether, diglycerin polyglycidyl ether, polyglycerin 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-added bisphenol A type diglycidyl ether, propylene oxide-added bisphenol A type diglycidyl ether, and hydrides of these condensates; and aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether.

[0060] Among these, from the viewpoint of curability and liquefaction, methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, ethylene oxide-added bisphenol A type diglycidyl ether, propylene oxide-added bisphenol A type diglycidyl ether, polyethylene glycol diglycidyl ether, and 1-phenoxy-1,4-(oxyranylmethoxy)-3,6,9,12-tetraoxatetradecane are preferred as glycidyl ether compounds.

[0061] Furthermore, glycidyl ether compounds having an ether structure are preferred from the viewpoint of adhesion. Specific examples include polyethylene glycol diglycidyl ether and 1-phenoxy-1,4-(oxyranylmethoxy)-3,6,9,12-tetraoxatetradecane. Glycidyl ether compounds may be used individually or in combination of two or more.

[0062] The amounts of ester compounds, hydrazine compounds, and glycidyl ether compounds added to the reaction system can be determined based on the molar ratio of the functional groups. The ester group of the ester compound is preferably 0.8 moles to 3.0 moles, more preferably 0.9 moles to 2.8 moles, and even more preferably 0.95 moles to 2.5 moles, per mole of the primary amine of the hydrazine compound. Furthermore, the amount of glycidyl groups in the glycidyl ether compound is preferably 0.8 moles to 2.0 moles, more preferably 0.9 moles to 1.5 moles, and even more preferably 0.95 moles to 1.4 moles, per mole of the primary amine in the hydrazine compound.

[0063] By controlling the amount of glycidyl group in the glycidyl ether compound added per mole of the primary amine in the hydrazine compound, compositions containing the compound represented by formula (1) and the compound represented by formula (3) can be produced simultaneously. Specifically, the glycidyl group of the glycidyl ether compound is preferably 0.1 to 3.0 moles, more preferably 0.3 to 2.0 moles, and even more preferably 0.5 to 1.0 moles, per mole of the primary amine of the hydrazine compound. In the above-mentioned methods for producing compounds and compositions, a solvent may be used to ensure that the reaction proceeds uniformly.

[0064] The solvent is not particularly limited, but examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.

[0065] The reaction temperature is preferably 10 to 100°C, and more preferably 40 to 90°C. A reaction temperature of 10°C or higher tends to accelerate the reaction and improve the purity of the resulting compound. Furthermore, a reaction temperature of 90°C or lower efficiently suppresses the polymerization reaction between glycidyl ether compounds, which also tends to improve the purity of the compound.

[0066] The reaction time is preferably 1 hour to 168 hours, more preferably 1 hour to 96 hours, and even more preferably 1 hour to 48 hours. After the reaction is complete, the resulting reaction product can be purified by known purification methods such as washing, extraction, recrystallization, and column chromatography. For example, the reaction solution dissolved in an organic solvent can be washed with water, and then the organic layer can be heated under atmospheric or reduced pressure to remove unreacted raw materials and organic solvents from the reaction solution and recover the target compound. The target compound can also be recovered by purification using column chromatography. The solvent used for the washing described above is not particularly limited as long as it can dissolve the residue of the raw materials, but 1-hexane, 1-pentane, and cyclohexane are preferred from the viewpoint of yield, purity, and ease of removal.

[0067] The organic solvent used in the extraction described above is not particularly limited as long as it can dissolve the target compound, but from the viewpoint of yield, purity, and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and the use of ethyl acetate, chloroform, toluene, and methyl isobutyl ketone is more preferred.

[0068] The packing material used in column chromatography is not particularly limited, but known materials such as alumina and silica gel can be used. The developing solvent is also not particularly limited, but known materials such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, and isopropanol can be used alone or in combination.

[0069] In the epoxy resin of this embodiment, (B) the curing agent is such that m in formula (2) and n in formula (3) are 2 or 3. This improves the crosslinking density during curing, allowing for the production of a tough cured product, and improving adhesion and reliability. In the epoxy resin composition of this embodiment, the content of the compound represented by formula (1), the compound represented by formula (2), or the compound represented by formula (3) is preferably 0.1% to 5% by mass, more preferably 0.2% to 4% by mass, and even more preferably 0.3% to 3% by mass, based on the total mass of the epoxy resin composition. This tends to achieve both viscosity stability and curability at high temperatures. The epoxy resin composition of this embodiment may optionally contain a curing agent other than the compound represented by formula (1), the compound represented by formula (2), or the compound represented by formula (3) below. The curing agent other than the compound represented by formula (1), the compound represented by formula (2), or the compound represented by formula (3) below is not particularly limited, but examples include amine-imide compounds other than the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3), amine-based curing agents, amide-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, catalytic curing agents, microencapsulated latent curing agents, thiol-based curing agents, and the like.

[0070] Examples of amine-based curing agents include, but are not limited to, aliphatic amines, aromatic amines, and amine adducts.

[0071] Aliphatic amines include, but are not limited to, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, and the like.

[0072] Examples of aromatic amines include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, KAYAHARD AA (manufactured by Nippon Kayaku Co., Ltd.), and EtaCure 100 Plus (manufactured by Mitsui Chemicals Fine Co., Ltd.).

[0073] As amine adducts, the reaction products of various amines listed above as amine compounds and the epoxy resin (A), epoxy reactive diluent, or other compounds that can react with amines can be used. Compounds that can react with amines are not particularly limited, but examples include alcohol compounds, alkyl halides, isocyanate compounds, and ester compounds.

[0074] The alcohol compounds are not particularly limited, but examples include aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, pentanol, hexanol, heptanol, and octanol, and ether-type alcohols having a polyethylene glycol structure. These may be used individually or in combination of two or more.

[0075] Regarding alkyl halides, there are no particular limitations, but examples include alkyl fluorides, alkyl chlorides, alkyl bromides, and alkyl iodides. More specifically, although there are no particular limitations, examples include chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, alkyl chlorides having ether functional groups, alkyl bromides, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, alkyl bromides having ether functional groups, iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, and alkyl iodides having ether functional groups.

[0076] The ester compounds are not particularly limited, but examples include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds. Specific examples of monocarboxylic acid ester compounds are not particularly limited, but examples include methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, isovalerate, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotate, methyl isocrotonate, methyl benzoyl methyl, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl, etc. Alternatively, ethyl esters, propyl esters, etc., may be used. Specific examples of dicarboxylic acid ester compounds are not limited to those mentioned above, but include, for example, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate. Alternatively, cyclic esters may be used instead. Specific examples of cyclic esters are not limited to those mentioned above, but include, for example, α-acetolactone, β-propionlactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone. The epoxy compound used in the synthesis of amine adducts is preferably in an amount of 0.1 to 1.0 equivalent, more preferably 0.1 to 0.75 equivalents, and even more preferably 0.1 to 0.5 equivalents, per equivalent of the active hydrogen of the amine compound.

[0077] Examples of amide-based curing agents include, but are not limited to, dicyandiamide and its derivatives, such as guanidine compounds, compounds obtained by adding acid anhydrides to amine compounds, and hydrazide compounds.

[0078] Examples of hydrazide compounds include, but are not limited to, succinate dihydrazide, adipic acid dihydrazide, phthalate dihydrazide, isophthalate dihydrazide, terephthalate dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleate dihydrazide.

[0079] Examples of guanidine compounds include, but are not limited to, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, and toluylguanidine. Examples of phenolic curing agents include, but are not limited to, phenol novolac resins, cresol novolac resins, phenol aralkyl resins, cresol aralkyl resins, naphthol aralkyl resins, biphenyl-modified phenol resins, biphenyl-modified phenol aralkyl resins, dicyclopentadiene-modified phenol resins, aminotriazine-modified phenol resins, naphthol novolac resins, naphthol-phenol cocondensed novolac resins, naphthol-cresol cocondensed novolac resins, and allyl acrylic phenol resins.

[0080] Examples of acid anhydride-based curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0081] As the active ester compound constituting the active ester-based curing agent, the active ester compound disclosed in Japanese Patent Publication No. 2004-277460 may be used, or a commercially available one may be used. Commercially available active ester compounds are not limited to the following, but for example, those containing a dicyclopentadienyldiphenol structure, acetylated phenol novolacs, and benzoylated phenol novolacs are preferred, and those containing a dicyclopentadienyldiphenol structure are particularly preferred. Examples of products containing a dicyclopentadienyldiphenol structure include, but are not limited to, EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), DC808 (manufactured by Japan Epoxy Resin Co., Ltd.) as an acetylated phenol novolac, and YLH1026 (manufactured by Japan Epoxy Resin Co., Ltd.) as a benzoylated phenol novolac.

[0082] Examples of catalytic curing agents include, but are not limited to, cationic thermosetting catalysts and BF3-amine complexes.

[0083] Examples of microencapsulated latent curing agents include, but are not limited to, Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP, and HXA-9382HP (manufactured by Asahi Kasei Corporation).

[0084] Examples of thiol-based curing agents include, but are not limited to, thiol compounds obtained by the esterification reaction of polyols such as trimethylolpropanetris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropanetris (β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate), and dipentaerythritol poly(β-thiopropionate) with thiol organic acids; alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexanedithiol, and 100-decanedithiol; polyethers containing terminal thiol groups; polythioethers containing terminal thiol groups; thiol compounds obtained by the reaction of epoxy compounds with hydrogen sulfide; and thiol compounds having terminal thiol groups obtained by the reaction of polythiol with epoxy compounds. In the epoxy resin composition of this embodiment, if a curing agent other than the compound represented by formula (1), the compound represented by formula (2), or the compound represented by formula (3) is included, the content thereof is preferably 0.1% to 10% by mass, more preferably 0.2% to 9% by mass, and even more preferably 0.3% to 8% by mass, based on the total mass of the epoxy resin composition. This tends to improve curability. The mass ratio of the compound represented by formula (1), formula (2), or formula (3) (compound B) to a curing agent other than the compound represented by formula (1), formula (2), or formula (3) (other curing agent) (other curing agent:compound B) is preferably 99:1 to 70:30, more preferably 97:3 to 75:25, and even more preferably 95:5 to 80:10. This tends to achieve both viscosity stability and curability at high temperatures. In the epoxy resin composition of this embodiment, the content of (B) curing agent is preferably 1 to 10% by mass, more preferably 2 to 9% by mass, and even more preferably 3 to 8% by mass.

[0085] ((C) Inorganic filler) The epoxy resin composition of this embodiment contains (C) an inorganic filler. In this embodiment, the inorganic filler (C) is something other than silica.

[0086] (C) There are no particular restrictions on the inorganic filler, but examples include powders such as calcium carbonate, clay, alumina such as aluminum oxide, aluminum nitride, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, or beads or glass fibers made by shaping these into spheres.

[0087] From the viewpoint of thermal conductivity, (C) the inorganic filler is preferably one or more selected from the group consisting of alumina, aluminum nitride, boron nitride, and silicon carbide, and is particularly preferably alumina.

[0088] Furthermore, from the viewpoint of permeability, it is preferable that the (C) inorganic filler contains one or more selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide, and alumina. The (C) inorganic filler may contain three or more types of fillers.

[0089] In the epoxy resin composition of this embodiment, the content of (C) inorganic filler is preferably 68.5 to 90% by mass. More preferably 69 to 88% by mass, and even more preferably 70 to 86% by mass.

[0090] In the epoxy resin composition of this embodiment, setting the content of (C) inorganic filler to 68.5% by mass or more tends to easily yield effects of reducing the coefficient of thermal expansion and improving temperature cycle resistance. Furthermore, in the epoxy resin composition of this embodiment, setting the content of (C) inorganic filler to 90% by mass or less tends to suppress the increase in viscosity of the epoxy resin composition, resulting in good fluidity, permeability, and dispensability. In particular, from the viewpoint of improving temperature cycle resistance, a higher lower limit for the content of (C) inorganic filler is preferable.

[0091] In this embodiment, even if the content of (C) inorganic filler is increased as described above, it is possible to maintain the epoxy resin composition at a low viscosity.

[0092] (C) The average particle size of the inorganic filler is preferably 0.01 μm or more and 5 μm or less, more preferably 0.05 μm or more and 4 μm or less, and even more preferably 0.1 μm or more and 3 μm or less. (C) By setting the average particle size of the inorganic filler to 0.01 μm or more, the dispersibility in the epoxy resin is improved, thixotropic properties are less likely to be imparted to the epoxy resin composition, and the flow characteristics of the epoxy resin composition tend to improve. On the other hand, (C) by setting the average particle size of the inorganic filler to 5 μm or less, the sedimentation of the inorganic filler in the epoxy resin composition tends to be suppressed, and the permeability to fine gaps and fluidity of the epoxy resin composition tend to improve, thereby suppressing the occurrence of voids and unfilled areas. In this embodiment, the average particle size of (C) inorganic filler can be measured using a particle size analyzer and SEM by the method described in the examples below.

[0093] In this specification, the average particle size of the inorganic filler can be measured, for example, as follows. Specifically, the inorganic filler to be measured is added to a solvent (pure water) in an amount of 0.0001% to 5% by mass, along with 1% to 8% by mass of a surfactant. The mixture is then vibrated in an ultrasonic cleaner for 30 seconds to 5 minutes to disperse the inorganic filler. Approximately 3 mL of the dispersion is injected into a measuring cell and measured at 25°C. A laser diffraction particle size analyzer (e.g., LA920 (product name) from Horiba, Ltd.) is used to measure the volume-based particle size distribution. The average particle size is determined as the particle diameter (D50%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reaches 50%. For example, sodium hexametaphosphate can be used as the surfactant.

[0094] (C) The maximum particle size of the inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. (C) By setting the maximum particle size of the inorganic filler to 10 μm or less, there is a tendency to improve the permeability into narrow gaps. (C) The lower limit of the maximum particle size of the inorganic filler is not particularly limited, but for example, it is 3 μm. In this embodiment, the maximum particle size of (C) inorganic filler can be measured by the method described in the examples below.

[0095] In this specification, the maximum particle size of the inorganic filler can be measured, for example, as follows. The inorganic filler (C) to be measured is added to the solvent (pure water) in an amount ranging from 1% to 5% by mass, along with 1% to 8% by mass of surfactant. The mixture is then vibrated in an ultrasonic cleaner for 30 seconds to 5 minutes to disperse the inorganic filler. Approximately 3 mL of the dispersion is injected into a measurement cell and measured at 25°C. A laser diffraction particle size analyzer (Horiba, Ltd., LA920) is used to measure the volume-based particle size distribution. The maximum particle size is determined as the particle diameter (D100%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reaches 100%.

[0096] Whether an inorganic filler contains both the first and second particles can be confirmed, for example, by determining the volume-based particle size distribution (frequency distribution) of the inorganic filler. Specifically, if the volume-based frequency distribution of the inorganic filler shows peaks in both the range of 5 nm to less than 200 nm and the range of 0.2 μm to 5 μm, it can be said that the inorganic filler contains both the first and second particles. However, the confirmation method is not limited to the method described above.

[0097] Furthermore, there are no particular limitations on the method for determining the proportion of the first or second particles in the inorganic filler. For example, the particle size distribution (frequency distribution) based on the volume of the inorganic filler can be determined, the peaks corresponding to the first particles and the peaks corresponding to the second particles can be separated at the troughs between them, and the proportion of the first or second particles can be determined by dividing the volume of particles contained in each separated range by the total volume of the inorganic filler. If the composition of the liquid resin composition is known, the proportion of the first or second particles in the inorganic filler can be determined from the composition of the liquid resin composition. Note that the calculation method is not limited to the above method.

[0098] Furthermore, the particle size distribution of the inorganic filler (C) contained in the epoxy resin composition can also be measured by the following method: The epoxy resin composition containing the inorganic filler (C) is heated at 800°C for 4 hours, and the ash content is observed with a scanning electron microscope. From the resulting image, particle size distribution data can be obtained by determining the ratio of particle diameter to number of inorganic fillers (C), and the average particle size meter (D50%) of the inorganic filler (C) can be obtained.

[0099] ((D) Silica) The epoxy resin composition of this embodiment preferably further contains (D) silica from the viewpoint of permeability.

[0100] (D) The silica is not particularly limited, but examples include fused silica and crystalline silica.

[0101] In the epoxy resin composition of this embodiment, the total content of (C) inorganic filler and (D) silica is preferably 68.5 to 90% by mass. More preferably 69 to 88% by mass, and even more preferably 70 to 86% by mass.

[0102] In the epoxy resin composition of this embodiment, setting the total content of (C) inorganic filler and (D) silica to 68.5% by mass or more tends to easily yield effects of reducing the coefficient of thermal expansion and improving temperature cycle resistance. Furthermore, in the epoxy resin composition of this embodiment, setting the total content of (C) inorganic filler and (D) silica to 90% by mass or less tends to suppress the increase in viscosity of the epoxy resin composition, resulting in good fluidity, permeability, and dispensability. In particular, from the viewpoint of improving temperature cycle resistance, a higher lower limit for the total content of (C) inorganic filler and (D) silica is preferable.

[0103] When the epoxy resin composition of this embodiment contains (D) silica, the mass ratio of (C) inorganic filler to (D) silica ((C) inorganic filler:(D) silica) is preferably 99:1 to 80:20, more preferably 98:2 to 85:15, and even more preferably 96:4 to 83:17. When the mass ratio of (C) inorganic filler to (D) silica ((C) inorganic filler:(D) silica) is lower than 99:1, the permeability tends to be improved, and when the mass ratio of (C) inorganic filler to (D) silica ((C) inorganic filler:(D) silica) is higher than 80:20, the thermal conductivity tends to be improved.

[0104] (D) The average particle size of silica is preferably 80 nm or less, more preferably 65 nm or less, and even more preferably 55 nm or less. (D) There is no particular lower limit to the average particle size of silica, but it is preferably 5 nm or more. (D) By setting the average particle size of silica to 80 nm or less, it tends to be easier to suppress the settling of inorganic fillers in the epoxy resin composition, and the permeability and fluidity into fine gaps of the epoxy resin composition tend to be improved, thereby suppressing the occurrence of voids and unfilled areas. In this embodiment, the average particle size of (D) silica can be measured by the method described in the examples below.

[0105] In this specification, the average particle size of silica can be measured, for example, as follows. Specifically, silica to be measured is added to a solvent (pure water) in an amount of 0.0001% to 5% by mass, along with 1% to 8% by mass of a surfactant. The mixture is then vibrated in an ultrasonic cleaner for 30 seconds to 5 minutes to disperse the silica. Approximately 3 mL of the dispersion is injected into a measuring cell and measured at 25°C. A laser diffraction particle size analyzer (e.g., LA920 (product name) from Horiba, Ltd.) is used to measure the volume-based particle size distribution. The average particle size is determined as the particle diameter (D50%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reaches 50%. For example, sodium hexametaphosphate can be used as the surfactant.

[0106] When the epoxy resin composition of this embodiment contains (D) silica, it is preferable that it contains silica with a particle size of 100 nm or less. More preferably, it contains silica with a particle size of 80 nm or less, and even more preferably, silica with a particle size of 50 nm or less. Including silica with a particle size of 100 nm or less tends to improve permeability. The lower limit of the silica particle size is not particularly limited, but for example, it is 10 nm. In this embodiment, the particle size of silica can be measured by the method described in the examples below.

[0107] In this specification, the particle size of silica can be measured by the following method: By heating an epoxy resin composition containing silica at 800°C for 4 hours and observing the ash content with a scanning electron microscope, particle size distribution data can be obtained by determining the particle size and number-based ratio of silica from the resulting image, and an average particle size meter (D50%) of silica can be obtained.

[0108] (C) The inorganic filler and / or (D) silica may be surface-treated. (C) The inorganic filler may be surface-treated using a silane coupling agent.

[0109] Silane coupling agents are not particularly limited, but examples include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylicsilane coupling agents, aminosilane coupling agents, isocyanuratesilane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfidosilane coupling agents, and isocyanatesilane coupling agents.

[0110] (Other ingredients) The epoxy resin composition of this embodiment may further contain other compounding agents such as curing accelerators, flame retardants, silane coupling agents, mold release agents, and pigments, as needed. These can be appropriately selected as long as the effects of this embodiment are obtained. The flame retardant is not particularly limited, but examples include halides, phosphorus-containing compounds, nitrogen-containing compounds, and inorganic flame retardants.

[0111] (Physical properties of epoxy resin compositions) The epoxy resin composition of this embodiment preferably has a viscosity of 1.4 Pa·s or less at 100°C, more preferably 1.0 Pa·s or less, and even more preferably 0.5 Pa·s or less. The epoxy resin composition of this embodiment tends to have excellent flowability over a wide range when its viscosity at 100°C is within the above range. The lower limit of the viscosity of the epoxy resin composition of this embodiment at 100°C is not particularly limited, but for example, it is 0.05 Pa·s.

[0112] The method for controlling the viscosity at 100°C to the above range is not particularly limited, but examples include setting the SP value range of the epoxy resin to the above range, and using an amine adduct / amine imide compound as a curing agent. In this embodiment, the viscosity at 100°C (initial viscosity A as described in the examples below) can be specifically measured by the method described in the examples.

[0113] The epoxy resin composition of this embodiment preferably has a viscosity increase of 1.0 to 40.0 times after being left at 100°C for 60 minutes, more preferably 1.0 to 30.0 times, even more preferably 1.0 to 15.0 times, and even more preferably 1.0 to 5.0 times. The epoxy resin composition of this embodiment tends to have excellent flowability over a wide range by having the viscosity increase within the above range.

[0114] The range of viscosity increase after standing at 100°C for 60 minutes can be controlled, for example, by selecting an appropriate type and combination of curing agents (B). The viscosity increase is not particularly limited, but for example, using aromatic amine curing agents tends to decrease the viscosity increase, and when using amine adducts, adding an epoxy-based reactive diluent to the aromatic amine tends to decrease the viscosity increase. Furthermore, using decomposition-type latent curing agents in combination with these also tends to decrease the viscosity increase. More specifically, the viscosity can be controlled by using, for example, a combination of an amine compound or amine adduct containing an aromatic ring, ester group, sulfonyl group, etc., in its structure, and an amine imide compound.

[0115] Furthermore, the epoxy resin composition of this embodiment preferably has a viscosity of 0.01 Pa·s to 4.50 Pa·s after being left at 100°C for 60 minutes, more preferably 0.01 Pa·s to 4.00 Pa·s, and even more preferably 0.01 Pa·s to 3.50 Pa·s. The viscosity after standing at 100°C for 60 minutes can be measured using a rheometer (e.g., HAAKE® MARS (trade name), manufactured by Thermo Scientific). Specifically, in this embodiment, the viscosity after standing at 100°C for 60 minutes can be measured by the method described in the examples.

[0116] In this embodiment, the viscosity increase rate after standing at 100°C for 60 minutes can be specifically measured by the method described in the example.

[0117] The epoxy resin composition of this embodiment preferably has a reaction rate of 80% to 100% when cured at 165°C, more preferably 84% to 100%, even more preferably 85% to 100%, even more preferably 90% to 100%, and particularly preferably 95% to 100%. By setting the reaction rate of the epoxy resin composition of this embodiment within the above range, it exhibits excellent adhesion and reliability.

[0118] The reaction rate can be controlled, for example, by the type of curing agent used. Examples of highly reactive curing agents include aromatic amine curing agents, amine adducts, and decomposition-type latent curing agents. The reaction rate can be controlled to be higher by using these, or by combining multiple types of other curing agents, or by increasing the amount added.

[0119] The reaction rate when the epoxy resin composition of this embodiment is cured at 165°C can be calculated, for example, by using EXSTER6000 (product name, Hitachi High-Tech Science Corporation) to raise the temperature from 25°C to 300°C at a rate of 5°C / min and then calculating the total amount of heat generated in the temperature range of 100°C to 250°C. The calculation formula is as follows. In this embodiment, the reaction rate can be specifically measured by the method described in the examples. Initial heat generation A: DSC peak heat generation of epoxy resin composition Heat generation after curing B: DSC peak heat generation of epoxy resin composition after heating Reaction rate (%) = 100 × (Initial heat generation A - Heat generation after curing B) ÷ Initial heat generation A

[0120] <Method for producing epoxy resin composition> The epoxy resin composition of this embodiment can be manufactured, for example, by dry blending the components contained in the epoxy resin composition described above, or by adjusting them using equipment normally used for mixing polymer substances. The mixing equipment is not particularly limited, but examples include kneading equipment such as a Banbury mixer, Laboplast mill, single-screw extruder, twin-screw extruder, and sculpting machine.

[0121] The epoxy resin composition of this embodiment is preferably obtained, for example, by stirring and mixing each component contained in the epoxy resin composition described above using a rotational / revolving mixer (for example, "ARE-310" (product name) manufactured by Thinky Co., Ltd.), and then kneading it with a three-roll mixer.

[0122] Furthermore, it is preferable to prepare the epoxy resin by mixing and stirring it in advance, then disperse the inorganic filler (C) to prepare the dispersion, add the hardener, stir and mix with a rotating / revolving mixer, and then knead with a three-roller mixer. (B) When adding a hardener, it is preferable to add hardener B-1 and hardener B-2, then hardener B-3, stir and mix with a rotating / revolving mixer, and then knead with a three-roller mixer.

[0123] Furthermore, when using silicon carbide as an inorganic filler (C), it is preferable to mix it using a rotating / revolving mixer, a swivel mixer, etc., as it may damage the three-roll mixer.

[0124] <Application> The epoxy resin composition and cured product of this embodiment are useful as adhesives, encapsulants, fillers, insulating materials, sealing materials, prepregs, etc. As adhesives, they are useful as liquid adhesives, film adhesives, die bonding materials, etc. As encapsulants, they are useful as solid encapsulants, liquid encapsulants, film encapsulants, etc., and as liquid encapsulants, they are useful as underfill materials, potting materials, dam materials, etc. As insulating materials, they are useful as insulating adhesive films, insulating adhesive pastes, solder resists, etc.

[0125] Adhesives The adhesive of this embodiment includes the epoxy resin composition described above. The epoxy resin composition of this embodiment can be suitably used as an adhesive.

[0126] ≪Cured product≫ The cured product of this embodiment contains the epoxy resin composition described above. The cured product of this embodiment is obtained by curing the epoxy resin composition described above. The cured product of this embodiment can be suitably used as a encapsulant. Furthermore, the cured product of this embodiment can be suitably used as a semiconductor package.

[0127] ≪Sealing material≫ The encapsulant of this embodiment includes the cured product described above. The encapsulant of this embodiment is preferably a semiconductor encapsulant.

[0128] Semiconductor Packages The semiconductor package of this embodiment includes the cured product described above. The semiconductor package manufacturing method of this embodiment includes the step of manufacturing a semiconductor package using the epoxy resin composition described above. The process of manufacturing a semiconductor package using the epoxy resin composition described above may include the step of preparing the epoxy resin composition described above. The process of manufacturing a semiconductor package using the epoxy resin composition described above may involve appropriately molding the prepared epoxy resin composition and curing it by heating it at a predetermined temperature and time to manufacture the semiconductor package. [Examples]

[0129] The features of the present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited in any way by these. That is, the materials, amounts used, proportions, processing content, processing procedures, etc., shown in the following examples can be changed as appropriate, as long as they do not depart from the spirit of the present invention. Furthermore, the various manufacturing conditions and evaluation result values ​​in the following examples have meaning as preferred upper or lower limits in embodiments of the present invention, and the preferred range may be defined by a combination of the aforementioned upper or lower limits and the values ​​of the following examples or the values ​​of the examples themselves.

[0130] The measurement and evaluation methods in the examples and comparative examples are as follows.

[0131] [(1) Measurement of viscosity increase (viscosity stability)] For the epoxy resin compositions obtained in the examples and comparative examples described later, the dynamic viscosity η'-temperature curve was obtained when the epoxy resin composition was heated using a rheometer (HAAKE MARS, Thermo Scientific) at a constant measurement temperature (100°C), oscillation mode (f=1Hz), and an aluminum parallel plate (R=35mm). The initial viscosity A(η1) was obtained by averaging the viscosity values ​​from 0.95 minutes to 1.05 minutes after the start of measurement, within the first 5 minutes after the start of measurement. The viscosity after storage B(η2) was obtained by averaging the viscosity values ​​from 59.95 minutes to 60.05 minutes after the start of measurement. The viscosity increase rate of the epoxy resin composition was calculated using the following formula. Viscosity increase (η² / η¹) = Viscosity after storage B (η²) ÷ Initial viscosity A (η¹) The measurement time was measured starting 10 seconds after the epoxy resin composition was dropped onto a hot plate that had reached its flow temperature and was sandwiched between measurement plates. The lower the viscosity, the better the stability at high temperatures. The obtained viscosity was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The viscosity increase was less than 3.0 times. B: The viscosity increase was between 3.0 times and less than 10.0 times. C: The viscosity increase was between 10.0 times and less than 40.0 times. D: The viscosity increase was 40.0 times or more.

[0132] [(2) Measurement of reaction rate] The epoxy resin compositions obtained in the examples and comparative examples described later were heated from 25°C to 300°C at a rate of 1°C / min using EXSTER6000 (Hitachi High-Tech Science Corporation). The total amount of heat generated was calculated from the observed exothermic peaks and defined as the initial heat generation amount A. The epoxy resin compositions were then placed in a small high-temperature chamber (manufactured by ESPEC) at 165°C for 2 hours to obtain a cured product. The amount of heat generated from the cured product after curing (post-curing heat generation amount B) was similarly measured, and the change in heat generation from the initial amount was calculated as a percentage and defined as the reaction rate. The calculation formula was as follows.

[0133] Initial calorific value A: DSC peak calorific value of the compound Heat generation after curing B: DSC peak heat generation of the compound after heating Reaction rate (%) = 100 × (Initial heat generation A - Heat generation after curing B) ÷ Initial heat generation A The obtained response rates were evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The response rate was over 95%. B: The response rate was between 90% and 95%. C: The response rate was between 85% and less than 90%. D: The response rate was less than 85%.

[0134] [(3) Measurement of glass transition temperature] The epoxy resin compositions obtained in the examples and comparative examples described later were cured at 165°C for 2 hours, and the glass transition temperature (Tg) (°C) of the resulting cured product was measured as follows. Using a dynamic viscoelasticity analyzer RSA-G2 (manufactured by TA Instruments), a test piece measuring 35 mm in length, 10 mm in width, and 2 mm in thickness, cut from the resulting cured product, was heated at 5°C / min, and the storage modulus (MPa) and loss modulus (MPa) were measured. The temperature at which the tanδ was maximized was determined. The higher the glass transition temperature, the better the heat resistance.

[0135] [(4) Permeability measurement (flow type)] The epoxy resin compositions obtained in the examples and comparative examples described later were placed on a hot plate with two glass plates, each containing two 25 μm thick copper foils spaced 10 mm apart. The temperature of the glass plates was set to 110°C, and the epoxy resin composition removed from the chamber was dripped into the openings of the two glass plates. The time required for the epoxy resin composition to penetrate 20 mm was measured. The shorter the time required for penetration, the better the penetration performance, and the better the penetration performance, the better the ability to inject into large areas. The time obtained was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The arrival time was less than 300 seconds. B: The arrival time was between 300 seconds and 400 seconds. C: The arrival time was between 400 seconds and 500 seconds. D: The arrival time was 500 seconds or more.

[0136] [(5) Measurement and evaluation of thermal conductivity] The epoxy resin compositions obtained in the examples and comparative examples described later were cured at 165°C for 2 hours, and the resulting cured material was cut into 40 mm x 40 mm pieces to prepare test specimens. The thermal conductivity of the prepared test specimens was measured according to ASTM D5470-16 using a thermal conductivity measuring device (product name: SS-H40, manufactured by Bethel Co., Ltd.). The obtained thermal conductivity was evaluated according to the following evaluation criteria. Higher thermal conductivity indicates better heat dissipation performance in narrow gaps and over large areas of electronic components. [Evaluation Criteria] A: The thermal conductivity was 1.3 W / m·k or higher. B: The thermal conductivity was less than 1.3 W / m·k and greater than or equal to 1.1 W / m·k. C: The thermal conductivity was less than 1.1 W / m·k and greater than or equal to 0.9 W / m·k. D: The thermal conductivity was less than 0.9 W / m·k.

[0137] [(6) Average particle size of inorganic fillers] The average particle size of the inorganic filler was measured as follows. Specifically, the inorganic filler to be measured was added to a solvent (pure water) along with a surfactant of 1% to 8% by mass, in a range of 0.0001% to 5% by mass. The mixture was then vibrated in an ultrasonic cleaner for 30 seconds to 5 minutes to disperse the inorganic filler. Approximately 3 mL of the dispersion was injected into a measurement cell and measured at 25°C. A laser diffraction particle size analyzer (Horiba, Ltd., LA920 (product name)) was used to measure the volume-based particle size distribution. The average particle size was determined as the particle diameter (D50%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reached 50%. Sodium hexametaphosphate was used as the surfactant.

[0138] [(7) Maximum particle size of inorganic fillers] The maximum particle size of the inorganic filler was measured as follows: The inorganic filler (C) to be measured was added to the solvent (pure water) in an amount ranging from 1% to 5% by mass, along with 1% to 8% by mass of surfactant. The mixture was then vibrated in an ultrasonic cleaner for 30 seconds to 5 minutes to disperse the inorganic filler. Approximately 3 mL of the dispersion was injected into a measurement cell and measured at 25°C. A laser diffraction particle size analyzer (Horiba, Ltd., LA920) was used to measure the volume-based particle size distribution. The maximum particle size was determined as the particle diameter (D100%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reached 100%.

[0139] [(8) Average particle size of silica] The average particle size of silica was measured as follows: Silica, the substance to be measured, was added to a solvent (pure water) in an amount ranging from 0.0001% to 5% by mass, along with 1% to 8% by mass of a surfactant. The silica was dispersed by vibrating an ultrasonic cleaner for 30 seconds to 5 minutes. Approximately 3 mL of the dispersion was injected into a measurement cell and measured at 25°C. A laser diffraction particle size analyzer (Horiba, Ltd., LA920 (product name)) was used to measure the volume-based particle size distribution. The average particle size was determined as the particle diameter (D50%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reached 50%. Sodium hexametaphosphate was used as the surfactant.

[0140] [(9) Silica particle size] The silica particle size was measured using the following method. An epoxy resin composition containing silica was heated at 800°C for 4 hours, and the ash content was observed using a scanning electron microscope. From the resulting image, particle size distribution data was obtained by determining the ratio of silica particle size and number, thereby obtaining an average silica particle size meter (D50%).

[0141] [(10) SP value] In this embodiment, the solubility parameter (SP value) refers to the Hansen solubility parameter, which was determined using the Hansen solubility sphere method and the HSP calculation software HSPiP.

[0142] ((A) Epoxy resin) A-1: JER-630LSD (manufactured by Mitsubishi Chemical Corporation): SP value 22.7, p-aminophenol type epoxy resin: Yes A-2: EXA-830CRP (manufactured by DIC Corporation): SP value 22.0, p-aminophenol type epoxy resin: None A-3: YED-216 (manufactured by Mitsubishi Chemical Corporation): SP value 19.39, δD: 16.90, δP: 7.60, δH: 5.70, p-aminophenol type epoxy resin: None A-4:2-EH (2-ethylhexylglycidyl ether): SP value 17.36, δD: 16.20, δP: 4.60, δH: 4.20 A-5: DY-BP (manufactured by Yokkaichi Gosei Co., Ltd.): SP value 18.31, δD: 16.40, δP: 6.00, δH: 5.50, p-aminophenol type epoxy resin: None

[0143] ((B) Curing agent for epoxy resin) B-1A: DETDA (Etacure 300): A curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Chemicals Fine, Inc.) B-1B: DMTDA (Etacure 100 Plus (+)): Curing agent containing diethyltoluenediamine (manufactured by Mitsui Chemicals Fine, Inc.) B-1C:MBDA:4,4'-Methylenebis[N-(1-methylpropyl)aniline] (Kumiai Chemical Industry Co., Ltd.)

[0144] ((C) Inorganic filler) C-1A: Alumina (average particle size 0.25 μm, surface treated with KBM-403 (3-glycidoxypropyltrimethoxysilane)) C-1B alumina (average particle size 0.25 μm, surface treated with KBM-573 (N-phenyl-3-aminopropyltrimethoxysilane)) C-1C: Alumina (average particle size 0.9 μm) C-1D: Alumina (average particle size 0.4 μm) C-2A: Aluminum nitride filler (average particle size 0.9 μm) C-3A: Silicon carbide filler (average particle size 1.2 μm) C-4A: Boron nitride filler (average particle size 1.4 μm)

[0145] ((D) Silica) Silica microparticles (average particle size 0.05 μm, silica 100 nm or less: present)

[0146] <Preparation of inorganic fillers> (Inorganic filler (C-1C)) 100 g of alumina (average particle size 0.9 μm) and 3 g of KBM-403 (3-glycidoxypropyltrimethoxysilane) were mixed and stirred at room temperature for 10 minutes using a stirrer, and then aged for 24 hours to obtain an inorganic filler (C-1C).

[0147] (Inorganic filler (C-1D)) Inorganic filler (C-1D) was prepared using the same method as the inorganic filler (C-1C) described above, except that alumina (average particle size 0.9 μm) was replaced with alumina (average particle size 0.4 μm).

[0148] <Preparation of curing agent for epoxy resin> (Synthesis of compound (B-2A)) A 500 mL four-necked flask equipped with a reflux condenser and stirring blade was purged with nitrogen. 20 g of 1-butanol and 0.05 ml of diethyltoluenediamine (DETDA) were added, and the mixture was heated until the internal temperature reached 120°C. Then, using a dropping funnel, 0.025 ml of 2-ethylhexylglycidyl ether (2-EH) was added dropwise over 30 minutes. After the addition was complete, the reaction solution was heated and stirred at 120°C for 6 hours to complete the reaction. Using an evaporator, 1-butanol was removed from the resulting solution over 2 hours while maintaining the temperature at 80°C and the pressure at 15 mmHg or less, to obtain the compound (B-2A) represented by the following formula. [ka]

[0149] (Synthesis of compound (B-3A)) 1.94 g (0.019 mol) of ethyl propionate and 5.00 g (0.009 mol) of polyethylene glycol diglycidyl ether were weighed into a round-bottom flask, and the flask was heated in an oil bath until it reached 90°C. Next, 1.62 g (0.016 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the addition was complete, the mixture was stirred and allowed to react for 4 hours at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted starting materials by distillation, yielding the liquid product compound (B-3A). The structure of compound (B-3A) is as follows.

[0150] [ka]

[0151] (Synthesis of compound (B-3B)) 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of butyl glycidyl ether were weighed into a round-bottom flask, and the flask was heated in an oil bath until it reached 90°C. Next, 3.85 g (0.038 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the addition was complete, the mixture was stirred for 4 hours at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted starting materials by distillation, yielding the liquid product compound (B-3B). The structure of compound (B-3B) is as follows. [ka]

[0152] (Synthesis of compound (B-3C)) Dimethyl succinate 8.77 g (0.06 mol), 1-aminopiperidine 12.02 g (0.12 mol), 2-ethylhexylglycidyl ether 22.54 g (0.12 mol), and t-butyl alcohol 21.67 g (0.29 mol) were mixed to obtain a solution. This solution was reacted at 55°C for 4 days with stirring to obtain a reaction mixture. The obtained reaction mixture was concentrated under reduced pressure at 55°C to remove t-butyl alcohol, by-product alcohol, and unreacted starting materials by distillation, yielding a solid product. This product was dissolved in ethyl acetate and washed with water repeatedly using a separatory funnel to remove unreacted starting material residues. This organic layer was concentrated again under reduced pressure at 55°C to obtain a white amorphous solid amineimide compound K (compound (B-3C)): 33.05 g (yield 84.1%). The infrared absorption spectrum was measured using the method described above, yielding IR(KBr): 1570 cm⁻¹. -1The following measurements were obtained. Mass spectrometry revealed a peak at m / z = 655.8. This indicated that the amineimide compound (B-3C) shown in the following formula was obtained. [ka]

[0153] (Synthesis of compound (B-3D)) 1.94 g (0.019 mol) of ethyl propionate, 1.62 g (0.016 mol) of 1-aminopiperidine, and 10.47 g (0.0095 mol) of Denacol EX-861 were mixed to obtain a solution. This solution was reacted at 90°C for 4 hours with stirring to obtain a reaction mixture. The obtained reaction mixture was concentrated under reduced pressure at 80°C to remove by-product alcohol and unreacted raw materials by distillation, yielding a liquid amineimide compound (compound (B-3D)). The infrared absorption spectrum was measured using the method described above, yielding IR(KBr): 1570 cm⁻¹. -1 The following measurements were obtained. Mass spectrometry revealed a peak at m / z = 705.4. This indicated that the amineimide compound (B-3D) shown in the following formula was obtained. [ka]

[0154] [Example 1] Each component listed in Table 1 was placed in the proportions listed in Table 1 in a plastic stirring container, stirred and mixed in a rotating / revolving mixer (Sinky Co., Ltd. "ARE-310" (product name)), and then kneaded with a three-roll mill to obtain an epoxy resin composition. The obtained epoxy resin compositions were evaluated using the methods described above. The evaluation results are shown in Table 1.

[0155] [Examples 2-13 and Comparative Example 1] An epoxy resin composition was obtained in the same manner as in Example 1, except that the mixing ratio of each raw material was changed as shown in Tables 1 and 2. The obtained epoxy resin compositions were evaluated using the methods described above. The evaluation results are shown in Tables 1 and 2.

[0156] [Table 1]

[0157] [Table 2]

[0158] As shown in Table 1, the epoxy resin compositions obtained in the examples exhibited excellent curability and storage stability, as well as good penetration and heat dissipation performance in narrow gaps and large areas. On the other hand, the epoxy resin composition obtained in Comparative Example 1, which did not contain compounds of formulas (1) to (3), exhibited poor curability, and also did not exhibit good penetration and heat dissipation performance in narrow gaps and large areas.

Claims

1. (A) epoxy resin, (B) curing agent, and (C) inorganic filler, The inorganic filler (C) mentioned above is other than silica. An epoxy resin composition wherein the curing agent (B) comprises a compound represented by the following formula (1), formula (2), or formula (3). 【Chemistry 1】 (In formulas (1) to (3), R 1 Each independently represents a hydrogen atom, or an n-valent organic group having 1 to 15 carbon atoms, which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond; R 2 and R 3 Each independently represents an unsubstituted or substituted alkyl, aryl, or aralkyl group having 1 to 12 carbon atoms, or is linked to form a heterocycle having 7 or fewer carbon atoms; R 4 Each of these independently represents either a hydrogen atom or an n-valent organic group having 1 to 60 carbon atoms, which may contain an oxygen atom; n represents an integer from 1 to 3. 5 represents a nitrogen atom with a negative charge, R 6 (This represents a nitrogen atom with a positive charge.)

2. The epoxy resin composition according to claim 1, wherein the (C) inorganic filler is one or more selected from the group consisting of alumina, aluminum nitride, boron nitride, and silicon carbide.

3. The epoxy resin composition according to claim 1, wherein the inorganic filler (C) is alumina.

4. The epoxy resin composition according to claim 1, wherein the (C) inorganic filler comprises one or more selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide, and alumina.

5. The epoxy resin composition according to claim 1, wherein the content of the inorganic filler (C) is 68.5% by mass or more and 90% by mass or less.

6. The epoxy resin composition according to claim 1, further comprising (D) silica.

7. The epoxy resin composition according to claim 6, wherein the mass ratio of (C) inorganic filler to (D) silica ((C) inorganic filler:(D) silica) is 99:1 to 80:

20.

8. The epoxy resin composition according to claim 1, wherein the average particle size of the inorganic filler (C) is 0.01 μm or more and 5 μm or less.

9. The epoxy resin composition according to claim 1, wherein the maximum particle size of the inorganic filler (C) is 10 μm or less.

10. The epoxy resin composition according to claim 6, wherein the (D) silica comprises silica with a particle size of 100 nm or less.

11. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) comprises a p-aminophenol type epoxy resin.

12. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) comprises at least one epoxy resin having a solubility parameter (SP value) of 15 or more and 21 or less.

13. The epoxy resin composition according to claim 1, wherein the viscosity at 100°C is 1.4 Pa·s or less.

14. The epoxy resin composition according to claim 1, wherein the viscosity increase rate after being left at 100°C for 60 minutes is 1 to 40 times.

15. The epoxy resin composition according to claim 1, wherein the reaction rate when cured at 165°C is 85% or more and 100% or less.

16. A cured product of the epoxy resin composition according to any one of claims 1 to 15.

17. A sealing material comprising the cured product described in claim 16.

18. The encapsulating material according to claim 17, which is an encapsulating material for semiconductors.

19. An adhesive comprising the epoxy resin composition according to any one of claims 1 to 15.

20. A semiconductor package comprising the cured product described in claim 16.

21. A method for manufacturing a semiconductor package, comprising the step of manufacturing a semiconductor package using an epoxy resin composition according to any one of claims 1 to 15.

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