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

Abstract

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. [Solution] An epoxy resin composition containing (A) epoxy resin, (B) curing agent, and (C) inorganic filler, The (C) inorganic filler comprises at least one selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide. The average particle size of the inorganic filler (C) is 0.01 μm or more and 5 μm or less. The reaction rate when cured at 165°C is 90% or higher. An epoxy resin composition having an initial viscosity of 1.0 Pa·s or less at 100°C.

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 properties.

[0003] Patent Document 1 describes an epoxy resin composition using aluminum tris(acetylacetonate) as a curing accelerator and using alumina filler and spherical nano-sized boron nitride as an inorganic filler.

[0004] Patent Document 2 describes an epoxy resin containing silica particles as a filler.

[0005] 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.

[0006] The two-component epoxy resin composition can be cured at room temperature, but the epoxy resin and the curing agent are stored separately and used after weighing and mixing them as needed. Therefore, storage and handling are complicated. Moreover, since the usable time is limited, it cannot be premixed in large quantities in advance, resulting in an increase in the blending frequency and an inevitable decrease in efficiency.

[0007] For the purpose of solving the problems of such two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed so far. For example, an epoxy resin composition in which a curing agent for an epoxy resin is blended with the epoxy resin can be mentioned.

Prior Art Documents

Patent Documents

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-182815 [Patent Document 2] Japanese Patent Publication No. 2019-077771 [Overview of the project] [Problems that the invention aims to solve]

[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 has issues with viscosity at high temperatures, and therefore there is room for improvement in its penetration over narrow gaps and large areas.

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

[0015] In view of the above circumstances, the problem that the present invention aims to solve is 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. [Means for solving the problem]

[0016] The present invention includes the following embodiments. [1] An epoxy resin composition comprising (A) epoxy resin, (B) curing agent, and (C) inorganic filler, The (C) inorganic filler comprises at least one selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide. The average particle size of the inorganic filler (C) is 0.01 μm or more and 5 μm or less. The reaction rate when cured at 165°C is 90% or higher. An epoxy resin composition having an initial viscosity of 1.0 Pa·s or less at 100°C. [2] The epoxy resin composition according to [1] above, wherein the viscosity increase rate after being left at 100°C for 60 minutes is 1 to 10 times. [3] The epoxy resin composition according to [1] above, wherein the (C) inorganic filler further comprises alumina. [4] The epoxy resin composition according to [1] above, wherein the (C) inorganic filler is surface-treated with one or more selected from the group consisting of silane coupling agents and titanate coupling agents. [5] The epoxy resin composition according to [1] above, wherein the content of the inorganic filler (C) is 40 to 90% by mass. [6] The epoxy resin composition according to [5] above, wherein the inorganic filler (C) contains aluminum nitride and aluminum oxide, and the mass ratio of the aluminum nitride to the aluminum oxide is 80:20 to 20:80. [7] The epoxy resin composition according to [5] above, wherein the inorganic filler (C) contains boron nitride and aluminum oxide, and the mass ratio of the boron nitride to the aluminum oxide is 80:20 to 20:80. [8] The epoxy resin composition according to [5] above, wherein the inorganic filler (C) contains silicon carbide and aluminum oxide, and the mass ratio of the silicon carbide to the aluminum oxide is 80:20 to 20:80. [9] The epoxy resin composition according to [1] above, further containing (D) silica.

[10] The epoxy resin composition according to [9] above, wherein the average particle diameter of the silica (D) is 0.001 μm or more and 0.1 μm or less.

[11] The epoxy resin composition according to [9] above, wherein the total content of the inorganic filler (C) and the silica (D) is 78.5 to 90% by mass, and the mass ratio of the inorganic filler (C) to the silica (D) is 99.9:0.1 to 80:20.

[12] The epoxy resin composition according to [1] above, wherein the epoxy resin (A) contains an epoxy resin reactive diluent having a solubility parameter (SP value) of 15 or more and less than 20.

[13] The epoxy resin composition according to [1] above, wherein the curing agent (B) contains an amine imide compound.

[14] The epoxy resin composition according to [1] above, wherein the curing agent (B) contains at least one selected from the group consisting of the compounds represented by the following formula (4), the following formula (i), and the following formula (6).

Chemical formula

[15] The epoxy resin composition according to [1] above, wherein the curing agent (B) comprises an aromatic amine adduct (B-1), which is a reaction product of an aromatic amine compound and a reactive compound having a functional group that can react with the aromatic amine compound.

[16] The curing agent (B) comprises an aromatic amine adduct (B-1), which is a reaction product of an aromatic amine compound and a reactive compound having a functional group that can react with the aromatic amine compound. The epoxy resin composition according to [1] above, wherein the aromatic amine compound is represented by the following formula (1) or the following formula (2). [ka] (In formula (1), Rα and Rβ each independently represent a monovalent organic group or halogen having 1 to 20 carbon atoms, a and b each independently represent an integer from 0 to 4, and X represents a divalent organic group or single bond.) [ka] (In formula (2), Rγ independently represents a monovalent organic group or halogen having 1 to 20 carbon atoms, and c is an integer from 1 to 4.)

[17] A cured product of any of the epoxy resin compositions described in [1] to

[16] above.

[18] A sealing material comprising the cured product described above

[17] .

[19] The encapsulant described in

[18] above, which is an encapsulant for semiconductors.

[20] An adhesive comprising the epoxy resin composition described in any of the above [1] to

[16] . [twenty one] A semiconductor package containing the cured product described above

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

[16] . [Effects of the Invention]

[0017] According to the present invention, it is possible 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. [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] This embodiment is an epoxy resin composition containing (A) epoxy resin, (B) curing agent, and (C) inorganic filler, wherein (C) inorganic filler comprises at least one selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide. The average particle size of the inorganic filler (C) is 0.01 μm or more and 5 μm or less. The reaction rate when cured at 165°C is 90% or higher. The initial viscosity at 100°C is 1.4 Pa·s or less.

[0023] ((A) Epoxy resin) The epoxy resin composition of this embodiment contains an epoxy resin. 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 ol-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] As for the epoxy resin, you can use a single bisphenol F type epoxy resin, a combination of bisphenol F type epoxy resin and bisphenol A type epoxy resin, or a combination of bisphenol F type epoxy resin and naphthalene type epoxy resin. From the viewpoint of achieving both permeability and reliability, it is preferable that (A) 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 (A) of this embodiment may contain an epoxy resin reactive diluent. The epoxy resin reactive diluent is 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] For epoxy resin reactive diluents, it is preferable that the solubility parameter (SP value) is between 15 and 20. When an epoxy resin composition contains such an epoxy resin, it tends to result in an epoxy resin composition with superior injection properties and less clogging. (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.

[0027] 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).

[0028] (SP value) 2 =(δD) 2 +(δP) 2 +(δH) 2

[0029] The epoxy resins mentioned above 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), 1,4-cyclohexanedimethanol diglycidyl ether (SP value: 19.75, δD: 17.40, δP: 7.40, δH: 5.70), and hydrogenated bisphenol type A epoxy resin ( Examples include n-butyl glycidyl ether (SP value: 18.76, δD: 17.40, δP: 5.70, δH: 4.10), n-butyl glycidyl ether (SP value: 18.31, δD: 16.40, δP: 6.00, δH: 5.50), ethyl glycidyl ether (SP value: 19.00, δD: 16.40, δP: 7.30, δH: 6.20), polyethylene glycol diglycidyl ether: Denacol EX830 (SP value: 20.07, δD: 16.40, δP: 7.50, δH: 8.80), etc.

[0030] The epoxy resin content is not particularly limited, but the lower limit of the content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total mass of the epoxy resin composition. The upper limit of the content is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. By setting the epoxy resin content within the above range, high fluidity tends to be obtained.

[0031] ((B) Hardener) The epoxy resin composition of this embodiment contains (B) a curing agent.

[0032] In this embodiment, (B) the curing agent preferably contains an amine imide compound.

[0033] In this embodiment, it is preferable that the curing agent (B) contains at least one compound selected from the group consisting of compounds represented by formulas (4), (5), and (6) (hereinafter also referred to as "compound B").

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] (In formulas (4) to (6), 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.)

[0038] In equations (4), (5), and (6), 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.

[0039] In formulas (4), (5), and (6), 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.

[0040] 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.

[0041] In R1, examples of hydrocarbon groups include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, 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. Among these, linear, branched, or cyclic alkyl groups are preferred as R1, linear alkyl groups are more preferred, and methyl, ethyl, or propyl groups are even more preferred.

[0042] R1 may be a divalent organic group having 1 to 15 carbon atoms. Examples of such divalent organic groups include methylene, ethylene, propylene, 2,2-dimethylpropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, undecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, neopentylene, dimethylbutylene, methylhexylene, and ethylhexylene. Examples of linear or branched alkylene groups include dimethylhexylene, trimethylhexylene, methylheptylene, dimethylheptylene, trimethylheptylene, tetramethylheptylene, ethylheptylene, methyloctylene, methylnonylene, methyldecylene, methyldodecylene, methylundecylene, methyltridecylene, methyltetradecylene, and methylpentadecylene. Among these, methylene, ethylene, and propylene are preferred as R1.

[0043] 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 tends to improve the availability of raw materials.

[0044] 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.

[0045] 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. Among these, R2 and R3 are preferably cyclic alkyl groups. A cyclohexyl group is more preferably the cyclic alkyl group.

[0046] 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. Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl group (e.g., dimethylhydrazine) may be hazardous, including explosives, and may also be toxic to humans. By ensuring that the alkyl group in R2 and R3 has two or more carbon atoms, the use of raw materials with the aforementioned toxicity and other risks can be avoided.

[0047] 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. In addition, it tends to have superior penetration and heat dissipation performance in narrow gaps and large areas.

[0048] The aryl groups in R2 and R3 are not particularly limited, but examples include phenyl groups and naphthyl groups.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] R2 and R3 may be linked together to form a heterocycle with R6 (a positively charged nitrogen atom) having 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. Among these, a hexamethyleneimine ring in which R2, R3, and R6 are linked is preferred.

[0053] Furthermore, while the substituents are not particularly limited, 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.

[0054] In formulas (4), (5), and (6), 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, examples of hydrocarbon groups include linear, branched, or cyclic alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and ethylhexyl groups; alkenyl groups such as vinyl, propynyl, butynyl, pentynyl, hexynyl, octinyl, desinyl, 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.

[0055] In R4, the hydrocarbon group 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.

[0056] In R4, the hydrocarbon group may have a polyoxyalkylene skeleton. An example of a polyoxyalkylene skeleton is a polyoxyethylene skeleton.

[0057] Among these, the organic group represented by R4 in formula (4), formula (5), or formula (6) is preferably an alkyl group, an alkenyl group, or an aralkyl group, more preferably an alkyl group or an alkenyl group, and even more preferably a branched alkyl group or a branched alkenyl group. These preferred groups may have 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. Furthermore, the Tg of the cured product obtained using the compound tends to improve. Moreover, it tends to have superior penetration and heat dissipation performance in narrow gaps and large areas.

[0058] In R4, the number of carbon atoms in the organic group is 1 to 60, preferably 1 to 20, 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. Additionally, it tends to exhibit superior penetration and heat dissipation performance in narrow gaps and large areas.

[0059] Among the above, R4 in formulas (4), (5), or (6) 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 improve the curing performance of the compound. It also tends to have superior penetration and heat dissipation performance in narrow gaps and large areas.

[0060] In formula (4) or formula (5), R4 is more preferably a linear or branched C3-C12 alkyl group, a linear or branched C3-C12 alkyl group having a hydroxyl group, a linear or branched C3-C12 alkyl group having a polyoxyalkylene skeleton, and a linear or branched C3-C12 alkyl group having both a hydroxyl group and a polyoxyalkylene skeleton. Having such a group makes it easier to obtain a liquid compound with a more appropriate viscosity, and tends to further improve the curing performance of the compound. It also tends to further improve penetration and heat dissipation performance in narrow gaps and large areas.

[0061] In formulas (5) and (6), n is preferably 2 or 3. This improves the crosslinking density during curing, resulting in a tougher cured product with improved adhesion and reliability. It also tends to further improve penetration and heat dissipation performance in narrow gaps and large areas.

[0062] From the viewpoint of controlling the curing temperature or viscosity, compound B preferably contains multiple compounds represented by formula (4), formula (5), or formula (6). It is also possible to include multiple compounds with different structures represented by the same formula.

[0063] Particularly from the viewpoint of viscosity control, it is preferable that compound B contains both compounds represented by formula (4) and formula (6).

[0064] When multiple compounds represented by formulas (4), (5), or (6) are included, it is preferable that the content of the compound represented by formula (4) is between 0.1% by mass and 99.5% by mass relative to the total amount of compounds represented by formulas (4), (5), or (6). This tends to allow for easy control of viscosity. A composition containing multiple compounds represented by formulas (4), (5), or (6) can be obtained by mixing multiple compounds, or by simultaneously producing multiple compounds in the compound production method described later.

[0065] Compound B more preferably contains at least one compound selected from the group consisting of the compound represented by (B-3A) below (hereinafter also simply referred to as "compound (B-3A)"), the compound represented by (B-3B) below (hereinafter also simply referred to as "compound (B-3B)"), the compound represented by (B-3C) below (hereinafter also simply referred to as "compound (B-3C)"), and the compound represented by (B-3D) below (hereinafter also simply referred to as "compound (B-3D)"). When compound B contains the above compounds, it tends to have superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] The total content of the compound represented by formula (4), the compound represented by formula (5), or the compound represented by formula (6) is not particularly limited, but it is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 5% by mass, based on 100% by mass (total mass) of the resin composition, as these compounds tend to have superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0071] Furthermore, the content of the compound represented by formula (4), formula (5), or formula (6) 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.

[0072] The compounds represented by formula (4), formula (5), or formula (6) can be produced by reacting, for example, ester compounds, hydrazine compounds, and glycidyl ether compounds, although these are not limited to the following.

[0073] The ester compounds are not particularly limited, but examples include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds. These ester compounds may be used individually or in combination of two or more.

[0074] Specific examples of monocarboxylic acid ester compounds include methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl 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, and 4-t-butoxybenzoylmethyl. Ethyl esters and propyl esters may also be used.

[0075] Specific examples of dicarboxylic acid ester compounds include 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. Cyclic esters may also be used. Specific examples of cyclic esters include α-acetolactone, β-propionactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone. Diethyl esters and dipropyl esters may also be used.

[0076] 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.

[0077] 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.

[0078] The glycidyl ether compound is not particularly limited, but for example, monofunctional monoglycidyl ether compounds, bifunctional or polyglycidyl ether compounds, etc., can be used. The glycidyl ether compound may be used alone or in combination of two or more types.

[0079] Specific examples of monoglycidyl ether compounds include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, orthophenylphenol glycidyl ether, benzyl glycidyl ether, biphenylyl glycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, and 3-[diethoxy(methyl)silyl]propyl glycidyl ether.

[0080] Specific examples of polyglycidyl ether compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, and glycerin polyglycidyl ether. Examples include aliphatic polyglycidyl ethers such as glycidyl 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.

[0081] 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.

[0082] Furthermore, from the viewpoint of adhesion, epoxy resins having an ether structure are preferred. Specifically, it is preferable that the epoxy resin be at least one selected from the group consisting of n-butyl glycidyl ether, 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.

[0083] 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.

[0084] By controlling the amount of glycidyl group in the glycidyl ether compound added per mole of the primary amine in the hydrazine compound, a mixture containing the compound represented by formula (4) and the compound represented by formula (6) can be produced simultaneously.

[0085] 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.

[0086] 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.

[0087] 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 100°C or lower efficiently suppresses the polymerization reaction between glycidyl ether compounds, which also tends to improve the purity of the compound.

[0088] 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.

[0089] 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 ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred.

[0090] For column chromatography, known packing materials such as alumina and silica gel can be used. Furthermore, known developing solvents such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, and isopropanol can be used individually or in combination.

[0091] The epoxy resin composition of this embodiment may optionally contain curing agents other than the compounds represented by formula (4), formula (5), or formula (6). The curing agents other than the compounds represented by formula (4), formula (5), or formula (6) are not particularly limited, but examples include 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.

[0092] <Amine-based curing agent> Examples of amine-based curing agents include, but are not limited to, aliphatic amines, aromatic amines, and amine adducts.

[0093] 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.

[0094] 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.).

[0095] Examples of amine adducts include aromatic amine adducts (B-1), which are reaction products of aromatic amine compounds and reactive compounds having functional groups that can react with the aromatic amine compound. Examples of aromatic amine compounds include aromatic amine compounds (A-1) represented by the following formula (1) or formula (2). Includes.

[0096] [ka]

[0097] In formula (1), Rα and Rβ each independently represent a monovalent organic group or halogen having 1 to 20 carbon atoms, a and b each independently represent an integer from 0 to 4, and X represents a divalent organic group or single bond.

[0098] [ka]

[0099] In formula (2), Rγ represents a monovalent organic group or halogen having 1 to 20 carbon atoms, and c is an integer from 1 to 4.

[0100] The curing agent (B) of this embodiment, by including the above-described components, tends to exhibit excellent penetration after mixing with epoxy resin, and to achieve both curability and storage stability.

[0101] <Aromatic amine compound (A-1)> Aromatic amine compounds (A-1) are represented by the following formula (1) or formula (2).

[0102] [ka]

[0103] In formula (1), Rα and Rβ each independently represent a monovalent organic group or halogen having 1 to 20 carbon atoms, a and b each independently represent an integer from 0 to 4, and X represents a divalent organic group or single bond.

[0104] In Rα and Rβ, the monovalent organic group having 1 to 20 carbon atoms is preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. a and b are each independently, preferably integers between 0 and 2, and more preferably 0 or 1. In X, the divalent organic group preferably has one aromatic ring, and more preferably has one benzene ring.

[0105] Examples of aromatic amine compounds represented by formula (1) include, for example, 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-4-aminobenzoate, 2-fluoro-4-aminophenyl-4-aminobenzoate, 3-fluoro-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-3-methyl-4-aminobenzoate, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and 1,3-bis(3-aminophenoxy) Examples include benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, etc., and it is preferable to use one or more selected from the group consisting of these.

[0106] Among the above, from the viewpoint of achieving both curability and storage stability after mixing with epoxy resin, the aromatic amine compound represented by formula (1) preferably has -O-, -CO-, -C(=O)O-, or -C(=O)NH- as X, preferably has -CO-, -C(=O)O-, or -C(=O)NH- bonds, and more preferably has -C(=O)O- bonds.

[0107] [ka]

[0108] In formula (2), Rγ represents a monovalent organic group or halogen having 1 to 20 carbon atoms, and c is an integer from 1 to 4. In Rγ, the monovalent organic group having 1 to 20 carbon atoms is preferably having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. c is preferably an integer between 1 and 3, and more preferably 1 or 2.

[0109] Examples of aromatic amine compounds represented by formula (2) include diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, and others, and it is preferable to use one or more selected from the group consisting of these. Among the above, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene and 2,6-diamino-3,5-diethyltoluene) is preferred as the aromatic amine compound represented by formula (2) from the viewpoint of achieving both curability and storage stability after mixing with epoxy resin.

[0110] <Aromatic amine adduct (B-1)> Aromatic amine adduct (B-1) is a reaction product of an aromatic amine compound (A-1) and a reactive compound having a functional group that can react with aromatic amine compound (A-1).

[0111] Examples of functional groups in reactive compounds that can react with aromatic amine compounds (A-1) include -C(=O)OC(=O)- groups, carboxyl groups, sulfo groups, isocyanate groups, carbonyl groups, epoxy groups, fluoro groups, chloro groups, bromo groups, and iodine groups.

[0112] The reactive compound is preferably at least one compound selected from the group consisting of acid anhydrides, acid dianhydrides, carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, epoxy compounds, and alkyl halogenated compounds.

[0113] Examples of carboxylic acid compounds include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

[0114] Examples of sulfonic acid compounds include ethanesulfonic acid and p-toluenesulfonic acid.

[0115] Examples of isocyanate compounds include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates. Examples of aliphatic diisocyanates include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of alicyclic diisocyanates include isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,3-bis(2-isocyanatopropyl-2yl)cyclohexane. Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of aliphatic triisocyanates include 1,3,6-triisocyanate methylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl. Examples of polyisocyanates include polymethylene polyphenyl polyisocyanates and polyisocyanates derived from the diisocyanate compounds mentioned above. Polyisocyanates derived from the above-mentioned diisocyanates include isocyanurate-type polyisocyanates, biuret-type polyisocyanates, urethane-type polyisocyanates, allohanate-type polyisocyanates, and carbodiimide-type polyisocyanates. Examples of urea compounds include urea, methylurea, dimethylurea, ethylurea, and t-butylurea.

[0116] The epoxy compound used may be a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof. Examples of monoepoxy compounds include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate. Examples of polyvalent epoxy compounds include bisphenol-type epoxy compounds obtained by glycidly fermenting bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A; epoxy compounds obtained by glycidly fermenting divalent phenols such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; epoxy compounds obtained by glycidly fermenting trisphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; and epoxy compounds obtained by glycidly fermenting tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of compounds include: novolac-type epoxy compounds obtained by glycidylating novolacs such as phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and brominated bisphenol A novolac; aliphatic ether-type epoxy compounds obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol; ether ester-type epoxy compounds obtained by glycidylating hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid; ester-type epoxy compounds obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl-type epoxy compounds such as epoxy compounds obtained by glycidylating amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and epoxy compounds obtained by glycidylating amine-type epoxy compounds such as triglycidyl isocyanurate; and alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0117] Among the above, epoxy compounds are preferred as the reactive compound from the viewpoint of excellent curability and storage stability, and epoxy compounds having one glycidyl group in the molecule are more preferred.

[0118] The total chlorine content of the epoxy compound is preferably 400 ppm or less, from the viewpoint of achieving both high curability and storage stability. More preferably 300 ppm or less, even more preferably 200 ppm or less, particularly preferably 180 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, particularly more preferably 80 ppm or less, and even more preferably 50 ppm or less. In this embodiment, the total chlorine content refers to the total amount of organic and inorganic chlorine contained in the compound, and is a value based on the mass of the compound. Of the total chlorine, the chlorine contained in the 1,2-chlorohydrin group is generally called hydrolyzable chlorine. The amount of hydrolyzable chlorine in the epoxy compound used in this embodiment is preferably 50 ppm or less, more preferably 0.01 to 20 ppm, and even more preferably 0.05 to 10 ppm. A hydrolyzable chlorine amount of 50 ppm or less is advantageous for achieving both high curability and storage stability, and is preferred because it tends to exhibit excellent electrical properties. In this embodiment, when it is desired to reduce the total chlorine content of the epoxy compound, examples include a method of performing a dechlorination reaction using a base catalyst in a non-proton solvent and then purifying the epoxy compound by washing with water, or a method of performing a dechlorination reaction using a metal amide compound such as a bis(trialkylsilyl)amide metal salt as a catalyst and then purifying the epoxy compound by washing with water.

[0119] Aromatic amine adduct (B-1) is a reaction product of an aromatic amine compound (A-1) and a reactive compound having a functional group that can react with aromatic amine compound (A-1). The aromatic amine adduct (B-1) used in this embodiment can be obtained, for example, by reacting 1 to 5 moles of an aromatic amine compound (A-1) with 1 to 5 moles of a reactive compound (e.g., an epoxy compound) at a temperature of, for example, 50 to 250°C for 0.1 to 24 hours, in the presence of a solvent as needed, and removing the unreacted aromatic amine compound (A-1) and solvent as needed. The solvents used here are not particularly limited, but examples include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; and water. These solvents may be used in combination. Furthermore, when using an aromatic amine compound (A-1) that is liquid at room temperature, a solvent may not be necessary.

[0120] <Amid-based hardener> 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.

[0121] 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.

[0122] Examples of guanidine compounds include, but are not limited to, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, and toluylguanidine.

[0123] <Phenol-based curing agent> 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.

[0124] <Acid anhydride curing agent> 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.

[0125] <Activated ester-based curing agent> 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.

[0126] <Catalytic curing agent> Examples of catalytic curing agents include, but are not limited to, cationic thermosetting catalysts and BF3-amine complexes.

[0127] <Microencapsulated latent curing agent> 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).

[0128] <Thiol-based hardening agent> 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.

[0129] In the epoxy resin composition of this embodiment, if a curing agent other than the compound represented by formula (4), formula (5), or formula (6) is included, its content is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and even more preferably 3% by mass or more and 10% by mass or less, based on the total mass of the epoxy resin composition. This tends to further improve the curability.

[0130] The mass ratio of the compound represented by formula (4), formula (5), or formula (6) to the curing agent (B) other than the compound represented by formula (4), formula (5), or formula (6) is preferably 1:1 to 1:20, more preferably 1:2 to 1:18, and even more preferably 1:5 to 1:15. This tends to achieve both viscosity stability and flowability.

[0131] ((C) Inorganic filler) The epoxy resin composition of this embodiment contains (C) an inorganic filler. Note that (C) the inorganic filler does not contain silica.

[0132] The inorganic filler includes at least one selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide, from the viewpoint of thermal conductivity.

[0133] In addition to the above, inorganic fillers may also include, for example, powders such as calcium carbonate, clay, alumina such as aluminum oxide, silicon nitride, calcium silicate, potassium titanate, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, or beads or glass fibers formed from these materials.

[0134] 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. In the epoxy resin composition of this embodiment, the content of (C) inorganic filler is preferably 40 to 90% by mass. More preferably 50 to 88% by mass, and even more preferably 60 to 86% by mass.

[0135] By setting the inorganic filler content to 40% by mass or more, it tends to be easier to obtain effects such as a reduction in the coefficient of thermal expansion and an improvement in temperature cycle resistance. By setting the inorganic filler content to 90% by mass or less, it tends to suppress the increase in viscosity of the epoxy resin composition and result in good fluidity, permeability, and dispensability. In particular, from the viewpoint of improving temperature cycle resistance, a higher lower limit for the inorganic filler content is preferable.

[0136] In this embodiment, even when the inorganic filler content is increased as described above, it tends to be possible to maintain a low viscosity in the resin composition.

[0137] (C) The average particle size of the inorganic filler is 0.01 μm or more and 5 μm or less, preferably 0.05 μm or more and 4 μm or less, and more preferably 0.1 μm or more and 3 μm or less. Setting the average particle size of the inorganic filler to 0.01 μm or more improves dispersibility in the epoxy resin, makes it less likely for thixotropic properties to be imparted to the epoxy resin composition, and tends to improve the flow characteristics of the epoxy resin composition. On the other hand, setting it to 5 μm or less tends to make it easier to suppress the settling of the inorganic filler in the epoxy resin composition, and also improves the permeability to fine gaps and fluidity of the epoxy resin composition, which tends to suppress the occurrence of voids and unfilled areas. The average particle size can be measured using a particle size analyzer and SEM by the method described in the examples below.

[0138] (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. Setting the maximum particle size of the inorganic filler to 10 μm or less tends to improve penetration into narrow gaps.

[0139] The maximum particle size of the inorganic filler can be measured by the method described in the examples below. Specifically, the inorganic filler to be measured is added to a solvent (pure water) in a range of 1% 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 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 average particle diameter 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%.

[0140] (C) The inorganic filler contains aluminum nitride and aluminum oxide, from the viewpoint of achieving both thermal conductivity and fluidity, and the mass ratio of aluminum nitride to aluminum oxide is preferably 80:20 to 20:80, and more preferably 70:30 to 30:70.

[0141] The inorganic filler (C) contains boron nitride and aluminum oxide, from the viewpoint of achieving both thermal conductivity and fluidity, and the mass ratio of boron nitride to aluminum oxide is preferably 80:20 to 20:80, and more preferably 50:50 to 20:80.

[0142] Furthermore, from the viewpoint of achieving both thermal conductivity and fluidity, the content of (C) inorganic filler is preferably 78.5 to 90% by mass, and the (C) inorganic filler contains silicon carbide and aluminum oxide, with the mass ratio of silicon carbide to aluminum oxide being preferably 80:20 to 20:80, and more preferably 50:50 to 20:80.

[0143] ((D) Silica) The epoxy resin composition of this embodiment preferably further contains silica from the viewpoint of permeability. Examples of silica include fused silica and crystalline silica.

[0144] In the epoxy resin composition of this embodiment, the total content of (C) inorganic filler and (D) silica is preferably 78.5 to 90% by mass, more preferably 50 to 88% by mass, and even more preferably 60 to 86% by mass.

[0145] (C) By setting the total content of inorganic filler and (D) silica to 78.5% by mass or more, it tends to be easier to obtain the effect of reducing the coefficient of thermal expansion and improving temperature cycle resistance. By setting the total content of inorganic filler and (D) silica to 90% by mass or less, it tends to suppress the increase in viscosity of the epoxy resin composition and improve fluidity, permeability, and dispensability. In particular, from the viewpoint of improving temperature cycle resistance, a higher lower limit for the inorganic filler content is preferable.

[0146] When the epoxy resin composition of this embodiment contains (D) silica, the mass ratio of (C) inorganic filler to (D) silica is preferably 99.1:0.1 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 is lower than 99.1:0.1, the permeability tends to be improved, and when the mass ratio of (C) inorganic filler to (D) silica is higher than 80:20, the thermal conductivity tends to be improved.

[0147] (D) The average particle size of silica is preferably 0.1 μm or less, more preferably 0.07 μm or less, and even more preferably 0.05 μm or less. The lower limit is not particularly limited, but it is preferably 0.001 μm or more. Setting the average particle size of silica to 0.1 μm or less tends to suppress the sedimentation of silica in the epoxy resin composition, and also tends to improve the permeability and fluidity into fine gaps of the epoxy resin composition, thereby suppressing the occurrence of voids and unfilled areas. The average particle size of silica can be measured by the method described in the examples below.

[0148] 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, the particle size of the silica is 80 nm or less, and even more preferably 50 nm or less. Including silica with a particle size of 100 nm or less tends to improve permeability. The particle size of silica can be measured by the method described in the examples below.

[0149] (C) The inorganic filler and / or (D) silica may be surface-treated. The inorganic filler may be surface-treated using one or more selected from the group consisting of silane coupling agents and titanate coupling agents.

[0150] Examples of silane coupling agents 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.

[0151] More specifically, examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 8-glycidoxyoctyltrimethoxysilane.

[0152] More specifically, examples of titanate coupling agents include isopropyltriisostearoyl titanate, tetraisopropylbis(dioctyl phosphite) titanate, tetraoctylbis(ditridecyl phosphite) titanate, titanium tetraacetylacetonate, titanium diisopropoxybis(ethylacetoacetate), and titanium isostearate. Silane coupling agents or titanate coupling agents may be used individually or in combination of two or more.

[0153] (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.

[0154] Flame retardants are not particularly limited, but examples include halides, phosphorus-containing compounds, nitrogen-containing compounds, and inorganic flame retardants.

[0155] (Epoxy resin composition)

[0156] The epoxy resin composition of this embodiment preferably has an initial viscosity of 1.0 Pa·s or less at 100°C, preferably 0.8 Pa·s or less, and more preferably 0.5 Pa·s or less. 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 initial viscosity at 100°C and 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). Specific measurement methods can be described in the examples.

[0157] The epoxy resin composition of this embodiment preferably has a viscosity increase of 1 to 10 times, more preferably 1 to 8 times, more preferably 1 to 7 times, and even more preferably 1 to 5 times after being left at 100°C for 60 minutes. This range tends to result in excellent fluidity over a wide area.

[0158] 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 tends to decrease when using aromatic amine curing agents, and when using amine adducts, the viscosity tends to decrease when aromatic amines are added with epoxy-based reactive diluents. Furthermore, the viscosity tends to decrease when using decomposition-type latent curing agents in combination with these. 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.

[0159] The viscosity increase after standing at 100°C for 60 minutes is measured using a rheometer (HAAKE MARS, Thermo Scientific) after dropping the epoxy resin composition onto a measurement plate and measuring it 1 minute and 60 minutes after the sample temperature reaches 100°C (measurement conditions: aluminum parallel plate, R=35mm, 1Hz). The viscosity after 1 minute is defined as "η1," and the viscosity after 60 minutes is defined as "η2." The viscosity increase is calculated as η2 / η1. The specific measurement method can be determined by the method described in the examples.

[0160] The epoxy resin composition of this embodiment has a reaction rate of 90% or more when cured at 165°C. Preferably, the reaction rate when cured at 165°C is 90% to 100%, preferably 92% to 100%, more preferably 94% to 100%, and even more preferably 95% to 100%. By keeping it within the above range, the adhesion and reliability tend to be excellent.

[0161] 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.

[0162] 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. Specifically, it can be 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 Hardening rate (%) = 100 × (Initial heat generation A - Heat generation after hardening B) ÷ Initial heat generation A

[0163] <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 resin composition, or by adjusting them using equipment normally used for mixing polymer substances. Examples of mixing equipment include Banbury mixers, Laboplast mills, single-screw extruders, twin-screw extruders, and other kneading equipment.

[0164] The epoxy resin composition of this embodiment can be obtained, for example, by stirring and mixing each component contained in the resin composition in a rotating / revolving mixer (for example, "ARE-310" (product name) manufactured by Thinky Co., Ltd.), and then kneading it with a three-roll mixer.

[0165] Furthermore, when using silicon carbide as an inorganic filler (C), it is preferable to mix it using a rotating / revolving mixer, a swivel mixer, or the like, as it may damage the three-roll mixer.

[0166] <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.

[0167] Adhesives The adhesive of this embodiment comprises the epoxy resin composition of this embodiment. The epoxy resin composition of this embodiment can be suitably used as an adhesive.

[0168] ≪Cured product≫ The cured product of this embodiment comprises the epoxy resin composition of this embodiment. The cured product is obtained by curing the epoxy resin composition.

[0169] ≪Sealing material≫ The encapsulant of this embodiment includes the cured product of this embodiment. The cured product of this embodiment can be suitably used as an encapsulant. The encapsulant is preferably a semiconductor encapsulant.

[0170] Semiconductor Packages The semiconductor package of this embodiment includes the cured product of this embodiment. The cured product of this embodiment can be suitably used as a semiconductor package. The semiconductor package manufacturing method of this embodiment includes the step of manufacturing a semiconductor package using the epoxy resin composition of this embodiment. The process of manufacturing a semiconductor package using the epoxy resin composition of this embodiment may include the step of preparing the epoxy resin composition of this embodiment. The process for manufacturing a semiconductor package using the epoxy resin composition of this embodiment 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]

[0171] The present invention will be described in more detail using examples and comparative examples, but the present invention is not limited in any way by these examples. [(1) Measurement of viscosity (η2 / η1)] 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 on an aluminum parallel plate (R=35mm). The initial viscosity η1 was obtained by averaging the viscosity values ​​from 0.95 minutes to 1.05 minutes after the start of measurement. The viscosity after storage 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 was calculated using the following formula. Viscosity increase = Viscosity after storage η2 ÷ Initial viscosity 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 3.0 times or less. B: The thickening rate was between 3.0 times and 5.0 times. C: The viscosity increase was between 5.0 times and 10.0 times. D: The viscosity increase was more than 10.0 times.

[0172] [(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), and the total amount of heat generated was calculated from the observed exothermic peaks. Furthermore, measurements were taken similarly after immersion in a small high-temperature chamber (manufactured by ESPEC) at 165°C for 2 hours, and the change in heat generated from the initial state was calculated as a percentage. The calculation formula is as follows. 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 [Evaluation Criteria] A: Response rate of 95% or higher B: Response rate between 90% and 95% C: Response rate between 85% and less than 90% D: Response rate less than 85%

[0173] [(3) Flow rate measurement] A test specimen was prepared by fixing a glass plate in place of a semiconductor element on a glass substrate (26 mm wide x 75 mm long) with a 25 μm gap. Next, this test specimen was placed on a hot plate and the temperature of the gap between the two glass substrates was set to 110°C. Then, an epoxy resin composition was applied to one end of the glass plate, and the time (seconds) required for the resin to pass through the gap and reach a point 20 mm away was measured. The obtained time was evaluated according to the evaluation criteria below. 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. [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.

[0174] [(4) Measurement of thermal conductivity] Test specimens were prepared by cutting 40mm x 40mm pieces of cured epoxy resin composition, which had been cured at 165°C for 2 hours. The test specimens and thermal conductivity were 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. [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.

[0175] [(5) Measurement of average particle size (D50)] Inorganic fillers or epoxy resin compositions were dissolved in THF to a concentration of 0.1% by mass of inorganic fillers, and the average particle size (D50) was determined using a diffraction / scattering particle size distribution analyzer (LA-920) manufactured by Horiba, Ltd. For inorganic fillers with a particle size of 0.1 μm or less, the average particle size (D50) was determined using the above samples with a multi-sample nanoparticle measurement system (nanoSAQLA) manufactured by Otsuka Electronics Co., Ltd.

[0176] The materials used in the examples and comparative examples are described below. ((A) Epoxy resin) JER-630LSD: p-aminophenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation) EXA-830CRP: Bisphenol F type epoxy resin (manufactured by DIC Corporation) Reactive epoxy resin diluent with a solubility parameter (SP value) of 15 to 20. YED-216: 1,6-Hexanediol diglycidyl ether (manufactured by Mitsubishi Chemical Corporation) SP value 19.39 Epogosei 2EH: 2-Ethylhexylglycidyl ether (manufactured by Yokkaichi Synthetic Co., Ltd.) SP value: 17.36 DY-BP: n-butylglycidyl ether (manufactured by Yokkaichi Synthetic Co., Ltd.) SP value: 18.31

[0177] ((B) Curing agent for epoxy resin) EtaCure 100 Plus (+): A curing agent containing diethyltoluenediamine (manufactured by Mitsui Chemicals Fine, Inc.) EtaCure 300: A curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Chemicals Fine, Inc.) MBDA:4,4'-Methylenebis[N-(1-methylpropyl)aniline](Kumia) I Chemical Industry Co., Ltd.)

[0178] ((C) Inorganic filler) C-1: Silicon carbide filler (average particle size 1.2 μm) C-2: Aluminum nitride filler (average particle size 0.9 μm) C-3: Boron nitride filler (average particle size 1.4 μm) C-4A: Surface-treated alumina film (average particle size 0.25 μm, surface-treated with KBM-403, carbon content 0.2 wt.%) C-4B: Surface-treated alumina film (average particle size 0.25 μm, surface-treated with KBM-4803, carbon content 0.2 wt.%) C-4C: Surface-treated alumina film (average particle size 0.25 μm, surface-treated with KBM-573, carbon content 0.2 wt.%) ASFP-07S (average particle size 0.9 μm, manufactured by Denka Co., Ltd.) ASFP-40 (average particle size 0.4 μm, manufactured by Denka Co., Ltd.)

[0179] (D) Silica Y50SP-C2 (average particle size 0.05 μm, manufactured by Admatex Co., Ltd.) SO-E2 (average particle size 0.6 μm, manufactured by Admatex Co., Ltd.)

[0180] <Preparation of inorganic fillers> (Inorganic filler (C-4D)) 100g of ASFP-07S (average particle size 0.9μm) and 3g of KBM-403 (3-glycidoxypropyltrimethoxysilane) were mixed and stirred at room temperature for 10 minutes using a stirrer, and then aged at room temperature for 24 hours to obtain an inorganic filler (C-4D).

[0181] (Inorganic filler (C-4E)) Inorganic filler (C-4E) was prepared using the same method as the inorganic filler (C-4D) described above, except that ASFP-07S (average particle size 0.9 μm) was replaced with ASFP-40 (average particle size 0.4 μm).

[0182] (Inorganic filler (C-4F)) Inorganic filler (C-4F) was prepared using the same method as the inorganic filler (C-4D) described above, except that KBM-403 was replaced with titanium diisopropoxy bis(ethyl acetate).

[0183] <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 EtaCure 100(+) 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. From the resulting solution, 1-butanol was removed by distillation over 2 hours using an evaporator, while maintaining the temperature at 80°C and the pressure at 15 mmHg or less, to obtain compound (B-2A). Compound (B-2A) contained the structure (B-2A-1) shown below.

[0184] [ka]

[0185] (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 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). Compound (B-3A) also contained structures (B-3A-1) and (B-3A-2) as shown below.

[0186] [ka]

[0187] (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). Furthermore, compound (B-3B) also included structures (B-3B-1) and (B-3B-2) as shown below.

[0188] [ka]

[0189] (Synthesis of compound (B-3C)) 8.77 g (0.06 mol) of dimethyl succinate, 12.02 g (0.12 mol) of 1-aminopiperidine, 22.54 g (0.12 mol) of 2-ethylhexyl glycidyl ether, and 21.67 g (0.29 mol) of t-butyl alcohol were mixed to obtain a solution. This solution was reacted with stirring at 55 °C for 4 days to obtain a reaction solution. The obtained reaction solution was concentrated under reduced pressure at 55 °C to distill off t-butyl alcohol, by-produced alcohol, and unreacted raw materials, thereby obtaining a solid product. This product was dissolved in ethyl acetate, and the unreacted raw material residue was removed by repeating washing with water using a separatory funnel. This organic layer was concentrated again under reduced pressure at 55 °C to obtain a white amorphous solid compound (B-3C). Note that the compound (B-3C) also included the structures (B-3C-1) and (B-3C-2) shown below.

[0190] [Chemical formula]

[0191] (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 polyethylene glycol diglycidyl ether (PEGDGE) were mixed to obtain a solution. This solution was reacted with stirring at 90 °C for 4 hours to obtain a reaction solution. The obtained reaction solution was concentrated under reduced pressure at 80 °C to distill off by-produced alcohol and unreacted raw materials, thereby obtaining a liquid amine imide compound (B-3D).

[0192] [Chemical formula]

[0193] [Example 1]

[0194] (Examples 1 to 15 and Comparative Example 1) Each component described in Table 1 was put into a plastic stirring container in the blending amounts described in Table 1, stirred and mixed with a rotary-revolution mixer ("ARE-310" (trade name) manufactured by Shinki Co., Ltd.), and then kneaded with a three-roll mill to prepare an epoxy resin composition. In addition, in the examples and comparative examples, the epoxy resin (A) was prepared by mixing and stirring in advance, and an inorganic filler (C) was dispersed therein to prepare a dispersion liquid. Then, a curing agent (B) was added to the dispersion liquid and stirred and mixed with a rotary-revolution mixer. Thereafter, an epoxy resin composition was prepared by kneading with a three-roll mill.

[0195] Each of the obtained epoxy resin compositions was poured into a Teflon (registered trademark) mold and heated at 165°C for 2 hours to prepare a cured product. Table 1 shows the evaluation results of the resin compositions and cured products obtained in Examples 1 to 16 and Comparative Example 1.

[0196]

Table 1

[0197] As shown in Table 1, an epoxy resin composition containing any one of silicon carbide fillers (C-1), aluminum nitride fillers (C-2), and boron nitride fillers (C-3) having an average particle size of 0.01 μm or more and 5 μm or less as an inorganic filler and having an initial viscosity at 100°C of 1.0 Pa·s or less was excellent in fluidity and thermal conductivity as a cured product. On the other hand, since the epoxy resin composition described in Comparative Example 1 used a silica filler as an inorganic filler, the thermal conductivity of the cured product was low. Furthermore, the epoxy resin composition described in the examples had a thickening rate of 1 to 10 times after being left standing at 100°C for 60 minutes, was excellent in viscosity stability, and was particularly suitable for use as an underfill material used for sealing large-area semiconductor chips and the like. Furthermore, by further including alumina as an inorganic filler in the epoxy resin compositions described in Examples 4 to 16, the initial viscosity can be reduced, and as a result, the inorganic filler content can be increased, thereby improving the thermal conductivity.

Claims

1. An epoxy resin composition comprising (A) epoxy resin, (B) curing agent, and (C) inorganic filler, The (C) inorganic filler comprises at least one selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide. The average particle size of the inorganic filler (C) is 0.01 μm or more and 5 μm or less. The reaction rate when cured at 165°C is 90% or more. An epoxy resin composition having an initial viscosity of 1.0 Pa·s or less at 100°C.

2. 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 10 times.

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

4. The epoxy resin composition according to claim 1, wherein the inorganic filler (C) is surface-treated with one or more selected from the group consisting of silane coupling agents and titanate coupling agents.

5. The epoxy resin composition according to claim 1, wherein the content of the inorganic filler (C) is 40 to 90% by mass.

6. The epoxy resin composition according to claim 5, wherein the (C) inorganic filler comprises aluminum nitride and aluminum oxide, and the mass ratio of aluminum nitride to aluminum oxide is 80:20 to 20:

80.

7. The epoxy resin composition according to claim 5, wherein the (C) inorganic filler comprises boron nitride and aluminum oxide, and the mass ratio of boron nitride to aluminum oxide is 80:20 to 20:

80.

8. The epoxy resin composition according to claim 5, wherein the (C) inorganic filler comprises silicon carbide and aluminum oxide, and the mass ratio of silicon carbide to aluminum oxide is 80:20 to 20:

80.

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

10. The epoxy resin composition according to claim 9, wherein the average particle size of the (D) silica is 0.001 μm or more and 0.1 μm or less.

11. The epoxy resin composition according to claim 9, wherein the total content of the inorganic filler (C) and the silica (D) is 78.5 to 90% by mass, and the mass ratio of the inorganic filler (C) to the silica (D) is 99.9:0.1 to 80:

20.

12. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) comprises an epoxy resin reactive diluent having a solubility parameter (SP value) of 15 or more and 20 or less.

13. The epoxy resin composition according to claim 1, wherein the curing agent (B) comprises an amine imide compound.

14. The epoxy resin composition according to claim 1, wherein the curing agent (B) comprises at least one selected from the group consisting of compounds represented by the following formulas (4), (5), and (6). 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 (In formulas (4) to (6), 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 group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle having 7 carbon atoms or less; 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.)

15. The epoxy resin composition according to claim 1, wherein the curing agent (B) comprises an aromatic amine adduct (B-1), which is a reaction product of an aromatic amine compound and a reactive compound having a functional group that can react with the aromatic amine compound.

16. The curing agent (B) comprises an aromatic amine adduct (B-1), which is a reaction product of an aromatic amine compound and a reactive compound having a functional group that can react with the aromatic amine compound. The epoxy resin composition according to claim 1, wherein the aromatic amine compound is represented by the following formula (1) or the following formula (2). 【Chemistry 4】 (In formula (1), Rα and Rβ each independently represent a monovalent organic group or halogen having 1 to 20 carbon atoms, a and b each independently represent an integer from 0 to 4, and X represents a divalent organic group or single bond.) 【Transformation 5】 (In formula (2), Rγ independently represents a monovalent organic group or halogen having 1 to 20 carbon atoms, and c is an integer from 1 to 4.)

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

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

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

20. An adhesive comprising the epoxy resin composition according to any one of claims 1 to 16.

21. A semiconductor package comprising the cured product according to claim 17.

22. 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 16.

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