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

Abstract

The present invention provides epoxy resin compositions, cured products, encapsulants, adhesives, and semiconductor packages and methods for manufacturing the same, which exhibit excellent penetration and heat dissipation performance in narrow gaps and large areas, as well as excellent curability and storage stability. [Solution] The epoxy resin composition of the present invention comprises an epoxy resin (A), a curing agent (B), and an inorganic filler (C), wherein the curing agent (B) comprises an aromatic amine adduct (B-2), which is a reaction product of a reactive compound having a functional group capable of reacting with an aromatic amine compound (B-1) and the aromatic amine compound (B-1), and the inorganic filler (C) is other than silica.

Description

[Technical Field]

[0001] The present invention relates to epoxy resin compositions, cured products, encapsulants, adhesives, and semiconductor packages and methods for manufacturing the same. [Background technology]

[0002] Because epoxy resins have various properties when cured, they are used in a wide range of applications, such as paints, electrical and electronic insulating materials, and adhesives.

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

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

[0005] Currently, the epoxy resin compositions commonly used are so-called two-part epoxy resin compositions, in which the epoxy resin and curing agent are mixed at the time of use.

[0006] While two-component epoxy resin compositions can cure at room temperature, they require separate storage of the epoxy resin and curing agent, followed by weighing and mixing as needed before use. This makes storage and handling cumbersome. Furthermore, the limited usable time prevents pre-mixing large quantities, leading to frequent mixing and inevitably reducing efficiency.

[0007] To address the challenges of these two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed. For example, epoxy resin compositions in which a curing agent for epoxy resins is blended with the epoxy resin can be considered. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2016-108358 [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.

[0012] 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.

[0013] 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 and heat dissipation performance are also required for fine areas such as between densely packed fibers like carbon fibers and glass fibers, and in narrow gap areas of electronic components.

[0014] Patent Document 1 uses imidazole as a curing accelerator, and there are problems with viscosity stability at high temperatures, so there is room for improvement in penetration in narrow gaps and large areas.

[0015] Patent Document 2 uses silica particles with low thermal conductivity as a filler in a high content, so there is room for improvement in heat dissipation performance.

[0016] The problem to be solved by the present invention is to provide an epoxy resin composition, a cured product, a sealing material, an adhesive, and a semiconductor package and a manufacturing method thereof, which are excellent in penetration and heat dissipation performance in a narrow gap and a large area, and also excellent in curability and storage stability.

Means for Solving the Problems

[0017] The present invention includes the following aspects. [1] An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and an inorganic filler (C), wherein the curing agent (B) includes a reactive compound having a functional group capable of reacting with an aromatic amine compound (B-1), and an aromatic amine adduct (B-2) which is a reaction product of the aromatic amine compound (B-1), and the inorganic filler (C) is other than silica, the epoxy resin composition.

[0018] [2] The epoxy resin composition according to [1], wherein the thermal conductivity of the inorganic filler (C) is 2.0 W / m·K or more.

[0019] [3] The epoxy resin composition according to [1] or [2], wherein the aromatic amine compound (B-1) includes at least one selected from the group consisting of an aromatic amine compound represented by the following formula (1) and an aromatic amine compound represented by the following formula (2).

[0020]

Chemical formula

[0021] (In formula (1), R α and Rβ Each of the following independently represents a monovalent organic group or halogen with 1 to 20 carbon atoms, a and b are each independently integers from 0 to 4, and X represents a divalent organic group or single bond.

[0022] [ka]

[0023] (In formula (2), R γ Each of these independently represents a monovalent organic group or halogen with 1 to 20 carbon atoms, where c is an integer from 1 to 4.

[0024] [4] The epoxy resin composition according to any one of [1] to [3], wherein the reactive compound is an epoxy compound having one glycidyl group in its molecule.

[0025] [5] The epoxy resin composition according to any one of [1] to [4], wherein the content of the aromatic amine adduct (B-2) is 0.1% by mass or more and 10.0% by mass or less based on 100% by mass of the resin composition.

[0026] [6] The epoxy resin composition according to any one of [1] to [5], wherein the curing agent (B) further comprises at least one selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5).

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] (In formulas (3) to (5), 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 2 or 3. R5 represents a negatively charged nitrogen atom, and R6 represents a positively charged nitrogen atom.)

[0031] [7] The epoxy resin composition according to [6], wherein the total content of the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) is 0.1% by mass or more and 10.0% by mass or less, based on 100% by mass of the resin composition.

[0032] [8] The epoxy resin composition according to any one of [1] to [7], wherein the inorganic filler (C) comprises at least one selected from the group consisting of alumina, aluminum nitride, boron nitride, and silicon carbide.

[0033] [9] The epoxy resin composition according to any one of [1] to [8], wherein the inorganic filler (C) contains alumina.

[0034]

[10] The epoxy resin composition according to any one of [1] to [9], wherein the inorganic filler (C) comprises at least one selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide, and alumina.

[0035]

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

[10] , wherein the content of the inorganic filler (C) is 10.0% by mass or more and 90.0% by mass or less based on 100% by mass of the resin composition.

[0036]

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

[11] , further comprising silica (D).

[0037]

[13] The epoxy resin composition according to

[12] , wherein the silica (D) content is 0.05% by mass or more and 15.0% by mass or less based on 100% by mass of the resin composition, and the mass ratio of the inorganic filler (C) to the silica (D) (inorganic filler (C): silica (D)) is 99:1 to 80:20.

[0038]

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

[13] , wherein the average particle size of the inorganic filler (C) is 0.01 μm or more and 5 μm or less.

[0039]

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

[14] , wherein the maximum particle size of the inorganic filler (C) is 10 μm or less.

[0040]

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

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

[0041]

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

[16] , comprising an epoxy resin (A) having a solubility parameter (SP value) of 15.0 or more and 21.0 or less.

[0042]

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

[17] , wherein the content of the epoxy resin (A) is 5.0% by mass or more and 15.0% by mass or less based on 100% by mass of the resin composition.

[0043]

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

[18] , further comprising an epoxy-based reactive diluent (a).

[0044]

[20] The epoxy resin composition according to

[19] , comprising an epoxy reactive diluent (a) having a solubility parameter (SP value) of 15.0 or more and 21.0 or less.

[0045]

[21] The epoxy resin composition according to

[19] or

[20] , wherein the content of the epoxy-based reactive diluent (a) is 1.0% by mass or more and 10.0% by mass or less based on 100% by mass of the resin composition.

[0046]

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

[21] , wherein the viscosity increase rate after being left at 100°C for 60 minutes is 1.0 times or more and 10.0 times or less.

[0047]

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

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

[0048] A cured product comprising the epoxy resin composition described in any one of

[24] [1] to

[23] .

[0049] A sealing material containing the cured product described in

[25] and

[24] .

[0050]

[26] The encapsulant described in

[25] , for use in semiconductors.

[0051] An adhesive comprising an epoxy resin composition described in any one of

[27] [1] to

[23] .

[0052] A semiconductor package containing the cured product described in

[28]

[24] .

[0053] A method for manufacturing a semiconductor package, comprising the step of manufacturing a semiconductor package using an epoxy resin composition described in any one of

[29] [1] to

[23] . [Effects of the Invention]

[0054] 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, as well as excellent curability and storage stability. [Modes for carrying out the invention]

[0055] The embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail below.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] Epoxy resin compositions The epoxy resin composition of this embodiment (hereinafter also simply referred to as "resin composition") comprises an epoxy resin (A), a curing agent (B), and an inorganic filler (C), wherein the curing agent (B) comprises an aromatic amine adduct (B-2), which is a reaction product of a reactive compound having a functional group capable of reacting with an aromatic amine compound (B-1) and the aromatic amine compound (B-1), and the inorganic filler (C) is other than silica.

[0060] ((A) Epoxy resin) The epoxy resin composition of this embodiment includes epoxy resin (A). Any commonly used epoxy resin can be used without particular restrictions. For example, an epoxy resin having two or more epoxy groups in one molecule is preferred. One type of epoxy resin may be used alone, or two or more types may be used in combination.

[0061] Examples of epoxy resins 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 A type epoxy resin, ethylene oxide Examples include aminophenol-type epoxy resins such as side-addition type bisphenol F epoxy resin and p-aminophenol-type epoxy resin, and difunctional epoxy resins such as propylene oxide-addition type bisphenol F epoxy resin; trifunctional epoxy resins such as trisphenol-type epoxy resin, N,N-diglycidylaminobenzene-type epoxy resin, o-(N,N-diglycidylamino)toluene-type epoxy resin, triazine-type epoxy resin, ethylene oxide-addition type trisphenol-type epoxy resin, and propylene oxide-addition type trisphenol-type epoxy resin; tetrafunctional epoxy resins such as 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.Furthermore, epoxy resins modified with isocyanates or the like can also be used in combination. These may be used individually or in combination of two or more.

[0062] As for the epoxy resin, a single bisphenol F type epoxy resin, a combination of a bisphenol F type epoxy resin and a bisphenol A type epoxy resin, and a combination of a bisphenol F type epoxy resin and a naphthalene type epoxy resin can also be used.

[0063] The epoxy resin preferably contains at least one selected from the group consisting of bisphenol F type epoxy resin, aminophenol type epoxy resin, and tetraglycidyldiaminodiphenylmethane type epoxy resin, more preferably contains an aminophenol type epoxy resin, and even more preferably contains a p-aminophenol type epoxy resin. When the epoxy resin composition contains the above epoxy resins, it tends to have superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curing properties and storage stability.

[0064] The epoxy resin content is preferably 5.0% to 15.0% by mass, more preferably 7.0% to 13.0% by mass, even more preferably 8.0% to 12.0% by mass, and even more preferably 9.0 parts by mass to 11.0% by mass, based on 100% by mass (total mass) of the resin composition. By setting the epoxy resin content within the above range, higher fluidity tends to be obtained.

[0065] ((a) Epoxy-based reactive diluents) The epoxy resin composition of this embodiment preferably further contains an epoxy-based reactive diluent. When the epoxy resin composition contains an epoxy-based reactive diluent, it tends to have superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curing properties and storage stability.

[0066] Examples of the epoxy-based reactive diluents mentioned above include 2-ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, 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, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol. Examples include diglycidyl ether, neopentyl glycol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, vinylcyclohexene dioxide, jER(registered trademark)-YX8000D (trade name, hydrogenated bisphonol type A epoxy resin, manufactured by Mitsubishi Chemical Corporation), SR-8EGS (trade name, manufactured by Sakamoto Pharmaceutical Co., Ltd.), 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.

[0067] The epoxy-based reactive diluent preferably contains at least one selected from the group consisting of n-butyl glycidyl ether, ethylhexyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphonol type A epoxy resin. When the epoxy resin composition contains the above-mentioned epoxy-based reactive diluent, it tends to exhibit superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curing and storage stability.

[0068] The content of the epoxy-based reactive diluent is preferably 1.0% to 10.0% by mass, more preferably 2.0% to 9.0% by mass, and even more preferably 3.0% to 8.0% by mass, based on 100% by mass (total mass) of the resin composition. By setting the content of the epoxy-based reactive diluent within the above range, higher fluidity tends to be obtained.

[0069] The epoxy resin composition of this embodiment more preferably includes an epoxy resin having a solubility parameter (SP value) of 15.0 or more and 21.0 or less among the epoxy resins described above. The epoxy resin composition more preferably includes an epoxy-based reactive diluent having an SP value of 15.0 or more and 21.0 or less among the epoxy-based reactive diluents described above. When the epoxy resin composition includes at least one selected from the group consisting of such epoxy resins and epoxy-based reactive diluents, an epoxy resin composition with superior injection properties without clogging can be obtained.

[0070] (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.

[0071] 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).

[0072] (SP value) 2 =(δD) 2 +(δP) 2 +(δH) 2

[0073] Examples of the epoxy resins mentioned above include bisphenol F type epoxy resin (SP value: 21.95, δD: 19.5, δP: 7.7, δH: 6.5), p-aminophenol type epoxy resin (SP value: 22.69, δD: 19.2, δP: 8.8, δH: 8.3), and tetraglycidyldiaminodiphenylmethane type epoxy resin (SP value: 22.30, δD: 19.6, δP: 7.3, δH: 7.7).

[0074] Examples of the epoxy-based reactive diluents mentioned above include 1,6-hexanediol diglycidyl ether (SP value: 19.39, δD: 16.90, δP: 7.60, δH: 5.70), ethylhexyl glycidyl 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 (jER(registered trademark)-YX80 Examples include 00D (product name), 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), and polyethylene glycol diglycidyl ether (Denacol® EX830 (product name), SP value: 20.07, δD: 16.40, δP: 7.50, δH: 8.80).

[0075] In the epoxy resin and epoxy-based reactive diluent, the SP value is preferably 15.5 or more and 19.5 or less. δD is preferably 13.0 or more and 18.0 or less, more preferably 14.0 or more and 18.0 or less. δP is preferably 1.0 or more and 8.0 or less, more preferably 2.0 or more and 7.6 or less. δH is preferably 1.0 or more and 7.0 or less, more preferably 2.0 or more and 6.0 or less. When all of the SP value, δD, δP, and δH are within the above ranges in at least one selected from the group consisting of an epoxy resin and an epoxy-based reactive diluent, a higher fluidity tends to be obtained.

[0076] ((B) Curing agent) The epoxy resin composition of the present embodiment contains a curing agent (B). The curing agent (B) may be used alone or in combination of two or more.

[0077] The curing agent (B) includes a reactive compound having a functional group capable of reacting with the aromatic amine compound (B-1) and an aromatic amine adduct (B-2) which is a reaction product of the reactive compound with the aromatic amine compound (B-1).

[0078] The aromatic amine compound (B-1) preferably includes at least one selected from the group consisting of the aromatic amine compound represented by the following formula (1) and the aromatic amine compound represented by the following formula (2). The aromatic amine compound (B-1) may be used alone or in combination of two or more.

[0079] [Chemical formula]

[0080] In formula (1), R α and R β each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and X represents a divalent organic group or a single bond. a and b are each independently preferably an integer of 1 to 4.

[0081] [ka]

[0082] In formula (2), R γ Each of these independently represents a monovalent organic group or halogen with 1 to 20 carbon atoms, where c is an integer from 1 to 4.

[0083] The curing agent of this embodiment, by including the above-described components, tends to exhibit superior penetration and heat dissipation after mixing with epoxy resin, and also achieves both superior curing properties and storage stability.

[0084] <Aromatic amine compounds represented by formula (1)> The aromatic amine compound (B-1) preferably includes the aromatic amine compound represented by formula (1) above. The aromatic amine compound represented by formula (1) may be used individually or in combination of two or more types.

[0085] In formula (1), R α and R β In this, the monovalent organic group having 1 to 20 carbon atoms is preferably a monovalent organic group having 1 to 10 carbon atoms, more preferably a monovalent organic group having 1 to 5 carbon atoms, and even more preferably a monovalent organic group having 1 to 3 carbon atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. a and b are each independently, preferably integers between 0 and 2, and more preferably 0 or 1. In X, the number of carbon atoms in the divalent organic group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. Examples of divalent organic groups include divalent organic groups having one or more aromatic rings, divalent organic groups without aromatic rings, -O-, -CO-, -C(=O)O-, -SO2-, and -C(=O)NH-. The divalent organic group having one or more aromatic rings is preferably a divalent organic group having one aromatic ring, and more preferably a divalent organic group having one benzene ring.

[0086] Examples of aromatic amine compounds represented by formula (1) include 4-aminophenyl-4-aminobenzoate (APAB), trimethylenebis(4-aminobenzoate), 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'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 1,4-bis(4-aminophenoxy)ben Zene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)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- Examples include 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, and 1,4-bis(3-aminopropyldimethylsilyl)benzene. It is preferable to use at least one aromatic amine selected from the group consisting of these, represented by formula (1).

[0087] Among the above, from the viewpoint of having superior permeability and heat dissipation after mixing with epoxy resin, and achieving both superior curing and storage stability, the aromatic amine compound represented by formula (1) preferably has -O-, -CO-, -C(=O)O-, or -C(=O)NH- as X, more preferably has -CO-, -C(=O)O-, or -C(=O)NH-, and even more preferably has -C(=O)O-. The aromatic amine compound represented by formula (1) preferably contains 4-aminophenyl-4-aminobenzoate (APAB). When the aromatic amine compound represented by formula (1) contains 4-aminophenyl-4-aminobenzoate (APAB), it tends to exhibit superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0088] In formula (1), X may be a divalent organic group that does not have an aromatic ring. Examples of aromatic amine compounds represented by formula (1) include m-tolidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, and 4,4'-diamino-3,3'-5,5'-tetraethyldiphenylmethane. It is preferable to use at least one aromatic amine selected from the group consisting of these compounds as the aromatic amine represented by formula (1).

[0089] Among the above, 3,3'-diethyl-4,4'-diaminodiphenylmethane is more preferred as the aromatic amine compound represented by formula (1) from the viewpoint of having superior permeability and heat dissipation after mixing with epoxy resin, and achieving both superior curing and storage stability.

[0090] <Aromatic amine compounds represented by formula (2)> The aromatic amine compound (B-1) preferably includes the aromatic amine compound represented by formula (2) above. The aromatic amine compound represented by formula (2) may be used individually or in combination of two or more types.

[0091] In formula (2), R γ In this, the monovalent organic group having 1 to 20 carbon atoms is preferably a monovalent organic group having 1 to 10 carbon atoms, more preferably a monovalent organic group having 1 to 5 carbon atoms, and even more preferably a monovalent organic group having 1 to 3 carbon atoms. c is preferably an integer between 1 and 3, and more preferably 1 or 2.

[0092] Examples of aromatic amine compounds represented by formula (2) include diethyltoluenediamine, dimethylthiotoluenediamine, Etacure 300 (a curing agent containing dimethylthiotoluenediamine, manufactured by Mitsui Chemicals Fine, Inc.), and Etacure 100 Plus (a curing agent containing diethyltoluenediamine, manufactured by Mitsui Chemicals Fine, Inc.). Diethyltoluenediamine can be at least one selected from the group consisting of 2,4-diamino-3,5-diethyltoluene and 2,6-diamino-3,5-diethyltoluene. It is preferable to use at least one aromatic amine selected from the group consisting of these as the aromatic amine represented by formula (2).

[0093] Among the above, it is preferable that the aromatic amine compound represented by formula (2) includes at least one selected from the group consisting of diethyltoluenediamine and dimethylthiotoluenediamine, from the viewpoint of achieving superior permeability and heat dissipation after mixing with epoxy resin, as well as superior curing and storage stability.

[0094] <Aromatic amine adduct (B-2)> Aromatic amine adduct (B-2) is a reaction product of aromatic amine compound (B-1) and a reactive compound having a functional group that can react with aromatic amine compound (B-1). Aromatic amine adduct (B-2) may be used alone or in combination of two or more types.

[0095] (Reactive compound) The reactive compound has a functional group that can react with the aromatic amine compound (B-1). The reactive compound may be used alone or in combination of two or more. Examples of the above-mentioned functional groups 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. Among these, it is preferable that the functional group includes an epoxy group.

[0096] The reactive compound preferably contains at least one selected from the group consisting of acid anhydrides, acid dianhydrides, carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, epoxy compounds, and alkyl halogen compounds. When the reactive compound contains the above compounds, it tends to exhibit superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0097] Examples of carboxylic acid compounds include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

[0098] Examples of sulfonic acid compounds include ethanesulfonic acid and p-toluenesulfonic acid.

[0099] 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.

[0100] 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.

[0101] Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate.

[0102] Examples of aliphatic triisocyanates include 1,3,6-triisocyanate methylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl.

[0103] Examples of polyisocyanates include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above-mentioned diisocyanate compounds.

[0104] Examples of polyisocyanates derived from the above-mentioned diisocyanates include isocyanurate-type polyisocyanates, biuret-type polyisocyanates, urethane-type polyisocyanates, allohanate-type polyisocyanates, and carbodiimide-type polyisocyanates.

[0105] Examples of urea compounds include urea, methylurea, dimethylurea, ethylurea, and t-butylurea.

[0106] Examples of epoxy compounds include monoepoxy compounds, polyvalent epoxy compounds, and mixtures thereof.

[0107] Monoepoxy compounds are epoxy compounds that have one glycidyl group in their molecule. Examples of monoepoxy compounds include 2-ethyl glycidyl ether (EGE), n-butyl glycidyl ether (n-BGE), hexyl glycidyl ether, phenyl glycidyl ether, ethylhexyl glycidyl ether (EH), 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.

[0108] Polyvalent epoxy compounds are epoxy compounds that have two or more glycidyl groups in their molecule. Examples of polyvalent epoxy compounds include: bisphenol-type epoxy compounds obtained by glycidylating 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 glycidylating divalent phenols such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; epoxy compounds obtained by glycidylating trisphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; epoxy compounds obtained by glycidylating tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane; and phenol novolacs. Examples include novolac-type epoxy compounds obtained by glycidylating novolacs such as 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 (e.g., polyethylene glycol diglycidyl ether); 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.

[0109] Among the above, from the viewpoint of superior permeability and heat dissipation, as well as superior curability and storage stability, the reactive compound preferably contains an epoxy compound, and more preferably contains an epoxy compound having one glycidyl group in its molecule.

[0110] The monoepoxy compound preferably contains at least one selected from the group consisting of 2-ethylglycidyl ether (EGE), n-butylglycidyl ether (n-BGE), and ethylhexylglycidyl ether (EH). When the reactive compound contains the above monoepoxy compound, it tends to exhibit superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0111] The polyvalent epoxy compound preferably contains polyethylene glycol diglycidyl ether. When the reactive compound contains the above-mentioned polyvalent epoxy compound, it tends to exhibit superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0112] The total chlorine content of the epoxy compound is preferably 400 ppm or less, 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, as this provides superior permeability and heat dissipation, as well as better curing and storage stability. 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.

[0113] 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 ppm to 20 ppm, and even more preferably 0.05 ppm to 10 ppm. When the amount of hydrolyzable chlorine is 50 ppm or less, it tends to exhibit superior permeability and heat dissipation, as well as better curing and storage stability. It also 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.

[0114] Aromatic amine adduct (B-2) is a reaction product of aromatic amine compound (B-1) and a reactive compound having a functional group that can react with aromatic amine compound (B-1). The aromatic amine adduct (B-2) used in this embodiment can be obtained, for example, by reacting 1.0 mole to 5.0 moles of an aromatic amine compound (B-1) with 1.0 mole to 5.0 moles of a reactive compound (e.g., an epoxy compound) in the presence of a solvent as needed, at a temperature of 50°C to 250°C for 0.1 hours to 24 hours, and removing the unreacted aromatic amine compound (B-1) and solvent as needed.

[0115] Examples of solvents used here 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 individually or in combination of two or more. Furthermore, when using an aromatic amine compound (B-1) that is liquid at room temperature, a solvent may not be necessary.

[0116] The content of aromatic amine adduct (B-2) is preferably 0.1% to 10.0% by mass, more preferably 0.2% to 9.0% by mass, and even more preferably 0.3% to 8.0% by mass, based on 100% by mass (total mass) of the resin composition. By having the aromatic amine adduct (B-2) content within the above range, it is possible to achieve both viscosity stability and curability at high temperatures.

[0117] (The compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5)) The curing agent preferably further comprises at least one selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5).

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] In formulas (3) to (5), 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 30 carbon atoms, which may contain an oxygen atom; n represents 2 or 3. R5 represents a negatively charged nitrogen atom, and R6 represents a positively charged nitrogen atom.

[0122] In the compounds represented by formula (3), formula (4), and formula (5), R1 is presumed to contribute to the reduction of energy required for NN bond cleavage. R2 and R3 are presumed to contribute to the reduction of energy required for cleavage reactions due to steric hindrance-induced destabilization. R4 is presumed to contribute to the suppression of liquefaction of the compound and the reduction of the glass transition temperature of the resulting cured product.

[0123] The details of each unit are described below.

[0124] In the compounds represented by formula (3), formula (4), and formula (5), 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.

[0125] Examples of organic groups in R1 include hydrocarbon groups, groups in which hydrogen atoms bonded to carbon atoms in a hydrocarbon group are substituted by hydroxyl or carbonyl groups, or groups in which some carbon atoms in a hydrocarbon group are replaced by ester or ether bonds.

[0126] Examples of hydrocarbon groups in R1 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. Among these, R1 is preferably a linear, branched, or cyclic alkyl group, more preferably a linear alkyl group, and even more preferably a methyl, ethyl, or propyl group.

[0127] 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, R1 is preferably a methylene group, an ethylene group, or a propylene group.

[0128] In R1, the organic group may have other substituents. Examples of substituents 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.

[0129] In R1, the number of carbon atoms in the organic group is usually 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.

[0130] 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.

[0131] Examples of C1-C12 alkyl groups in R2 and R3 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. More preferably, the cyclic alkyl group is a cyclohexyl group.

[0132] In R2 and R3, the number of carbon atoms in the alkyl group is usually 1 to 12, preferably 2 to 10, and more preferably 5 to 10, independently of each other. Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl group (e.g., dimethylhydrazine) may be hazardous, including explosives, and may be toxic to humans. By ensuring that the alkyl group in R2 and R3 has two or more carbon atoms, it tends to be possible to avoid using raw materials that carry the aforementioned toxicity and other risks.

[0133] 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.

[0134] Examples of aryl groups in R2 and R3 include phenyl groups and naphthyl groups.

[0135] Examples of aralkyl groups in R2 and R3 include methylphenyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl groups.

[0136] Among these, R2 and R3 are preferably aralkyl groups, and more preferably methylphenyl groups (benzyl groups). This tends to further improve the curing performance of the compound. The number of carbon atoms in the aryl and aralkyl groups represented by R2 and R3 is preferably 6 to 20.

[0137] Examples of substituents on alkyl, aryl, or aralkyl groups in R2 and R3 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.

[0138] R2 and R3 may be linked together to form a heterocycle with R6 (a positively charged nitrogen atom) having 7 or fewer carbon atoms. Examples of heterocycles include four-membered rings such as azetidine rings; five-membered rings such as pyrrolidine rings, pyrrole rings, morpholine rings, and thiaidine rings; six-membered rings such as piperidine rings; and seven-membered rings such as hexamethyleneimine rings and azepine rings. Among these, the heterocycle is preferably a pyrrole ring, morpholine ring, thiaidine ring, piperidine ring, hexamethyleneimine ring, or azepine ring, and more preferably a 6-membered ring or a 7-membered ring. Having such a group makes it easier to obtain a liquid compound and tends to improve the curing performance of the compound. Among these, a hexamethyleneimine ring in which R2, R3, and R6 are linked is preferred.

[0139] Examples of substituents include alkyl groups, aryl groups, and the substituents at R2 and R3 mentioned above. Furthermore, when the heterocycle has an alkyl group as a substituent, a methyl group bonded to a carbon atom adjacent to R6 can be given as an example.

[0140] In the compounds represented by formula (3), (4), and (5), R4 independently represents either a hydrogen atom or an n-valent organic group having 1 to 30 carbon atoms, which may contain an oxygen atom. Examples of organic groups in R4 include hydrocarbon groups, groups in which hydrogen atoms bonded to carbon atoms in a hydrocarbon group are substituted 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 ester bonds, ether bonds, or silicon atoms.

[0141] Examples of hydrocarbon groups in R4 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.

[0142] In R4, the hydrocarbon group may include, for example, 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. Examples of organic groups containing a bisphenol skeleton include groups in which a polyoxyalkylene group is added to the hydroxyl group of each bisphenol skeleton.

[0143] In R4, the hydrocarbon group may have a polyoxyalkylene skeleton. An example of a polyoxyalkylene skeleton is a polyoxyethylene skeleton.

[0144] Among these, the organic group represented by R4 in the compound represented by formula (3) or formula (4) is preferably an alkyl group, an alkenyl group, or an aralkyl group, more preferably an alkyl group and an alkenyl group, and even more preferably a branched alkyl group and a branched alkenyl group. These preferred groups may have substituents. Having such groups makes it easier to obtain a liquid compound with appropriate viscosity, and tends to improve the curing performance of the compound. 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.

[0145] In R4, the number of carbon atoms in the organic group is usually 1 to 60, preferably 1 to 55, more preferably 1 to 50, and even more preferably 1 to 45. 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. Cured products obtained using such compounds tend to have a higher Tg. Having the number of carbon atoms in the organic group in R4 within this range also improves the availability of raw materials and tends to result in superior penetration and heat dissipation performance in narrow gaps and large areas.

[0146] Among the above, R4 in the compounds represented by formula (3) or formula (4) is preferably a linear or branched alkyl group having 3 to 12 carbon atoms, or a linear or branched alkenyl group having 3 to 6 carbon atoms. Having such a group makes it easier to obtain a liquid compound with appropriate viscosity, and tends to further improve the curing performance of the compound. It also tends to be superior in terms of penetration and heat dissipation performance in narrow gaps and large areas.

[0147] In the compounds represented by formula (3) or formula (4), 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.

[0148] In the compounds represented by formula (4) and formula (5), n is preferably 2 or 3. This improves the crosslinking density during curing, resulting in a tougher cured product, which tends to improve adhesion and reliability. It also tends to further improve penetration and heat dissipation performance in narrow gaps and large areas.

[0149] From the viewpoint of controlling the curing temperature or viscosity, the curing agent (B) preferably contains multiple compounds represented by formula (3), formula (4), or formula (5). It is also possible to include multiple compounds with different structures represented by the same formula.

[0150] Particularly from the viewpoint of viscosity control, it is preferable that the curing agent (B) contains both the compound represented by formula (3) and the compound represented by formula (5).

[0151] When a compound represented by formula (3), formula (4), and formula (5) is included in multiple quantities, their respective content ratios are as follows: The content of the compound represented by formula (3) is preferably 0.1% by mass or more and 99.5% by mass or less, relative to the total amount of the compounds represented by formula (3), formula (4), and formula (5). The content of the compound represented by formula (4) is preferably 0.1% by mass or more and 99.8% by mass or less, relative to the total amount of the compounds represented by formula (3), formula (4), and formula (5). The content of the compound represented by formula (5) is preferably 0.1% by mass or more and 99.8% by mass or less, relative to the total amount of the compounds represented by formula (3), formula (4), and formula (5). When the content ratios are within the above ranges, the viscosity tends to be easily controlled.

[0152] A mixture containing multiple compounds represented by formula (3), formula (4), and formula (5) can be obtained by mixing multiple compounds, or by simultaneously producing multiple compounds in the compound production method described below.

[0153] The total content of the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) tends to be superior in terms of penetration and heat dissipation performance in narrow gaps and large areas, as well as superior in curability and storage stability. Therefore, the total content is preferably 0.1% to 10.0% by mass, more preferably 0.5% to 7.0% by mass, even more preferably 1.0% to 6.0% by mass, and even more preferably 1.5% to 5.0% by mass, based on 100% by mass (total mass) of the resin composition.

[0154] The cured product (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)"). The compound represented by (B-3A) below corresponds to the compound represented by formula (5), the compound represented by (B-3B) below corresponds to the compound represented by formula (3), the compound represented by (B-3C) below corresponds to the compound represented by formula (4), and the compound represented by (B-3D) below corresponds to the compound represented by formula (5). When the cured product (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.

[0155] [ka]

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] The total content of compound (B-3A), compound (B-3B), compound (B-3C), and compound (B-3D) tends to be superior in terms of penetration and heat dissipation performance in narrow gaps and large areas, as well as superior in curability and storage stability. Therefore, the total content is preferably 0.1% to 10.0% by mass, more preferably 0.5% to 7.0% by mass, even more preferably 1.0% to 6.0% by mass, and even more preferably 1.5% to 5.0% by mass, based on 100% by mass (total mass) of the resin composition.

[0160] The compounds represented by formula (3), formula (4), or formula (5) can be produced, for example, by reacting ester compounds, hydrazine compounds, and glycidyl ether compounds.

[0161] Examples of ester compounds include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds. Ester compounds may be used individually or in combination of two or more.

[0162] 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, 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. Alternatively, ethyl esters and propyl esters may be used instead.

[0163] Examples of dicarboxylic acid ester compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dibutyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimerate, dimethyl suberate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate. Alternatively, cyclic esters may be used instead. Examples of cyclic esters include α-acetolactone, β-propionactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone. Alternatively, diethyl esters and dipropyl esters may be used instead.

[0164] Among these, from the viewpoint of curability and liquefaction, it is preferable that the ester compound contains at least one selected from the group consisting of 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, dibutyl 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.

[0165] Examples of hydrazine compounds 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.

[0166] Among these, from the viewpoint of curing properties and liquefaction, it is preferable that the hydrazine compound includes at least one selected from the group consisting of dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine. Furthermore, from the viewpoint of availability and safety, it is more preferable that the compound includes at least one selected from the group consisting of dibenzylhydrazine and 1-aminopiperidine. The hydrazine compound may be used alone or in combination of two or more.

[0167] Examples of glycidyl ether compounds that can be used include monofunctional monoglycidyl ether compounds and polyglycidyl ether compounds with two or more functions. Glycidyl ether compounds may be used individually or in combination of two or more.

[0168] Examples of monoglycidyl ether compounds include methyl glycidyl ether, 2-ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 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.

[0169] Examples of polyglycidyl ether compounds include 1,6-hexanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether. Examples include aliphatic polyglycidyl ethers such as glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, and sorbitol polyglycidyl ether; alicyclic polyglycidyl ether compounds such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, bisphenol S type diglycidyl ether, ethylene oxide-added bisphenol A type diglycidyl ether, propylene oxide-added bisphenol A type diglycidyl ether, and hydrogenated products of these condensates (e.g., hydrogenated bisphenol A type epoxy resin); and aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether.

[0170] Among these, glycidyl ether compounds that exhibit curability and liquefaction include methyl glycidyl ether, 2-ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether. Preferably, the material contains at least one selected from the group consisting of lysidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A type diglycidyl ether, hydrogenated bisphenol A type epoxy resin, 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.

[0171] Furthermore, from the viewpoint of adhesion, epoxy resins having an ether structure are preferred. Preferably, the epoxy resin having an ether structure contains at least one selected from the group consisting of 2-ethylglycidyl ether, n-butylglycidyl ether, ethylhexylglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, and 1-phenoxy-1,4-(oxyranylmethoxy)-3,6,9,12-tetraoxatetradecane.

[0172] 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.

[0173] The ester group of the ester compound is preferably 0.80 moles to 3.00 moles, more preferably 0.90 moles to 2.80 moles, and even more preferably 0.95 moles to 2.50 moles, per mole of the primary amine of the hydrazine compound.

[0174] Furthermore, the amount of glycidyl groups in the glycidyl ether compound is preferably 0.80 moles to 2.00 moles, more preferably 0.90 moles to 1.50 moles, and even more preferably 0.95 moles to 1.40 moles, per mole of the primary amine of the hydrazine compound.

[0175] 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 (3) and the compound represented by formula (5) can be produced simultaneously. Specifically, the glycidyl group of the glycidyl ether compound is preferably 0.1 moles to 3.0 moles, more preferably 0.3 moles to 2.0 moles, and even more preferably 0.5 moles to 1.0 mole, per mole of the primary amine of the hydrazine compound.

[0176] In the above-mentioned methods for producing compounds and compositions, a solvent may be used to ensure that the reaction proceeds uniformly.

[0177] Examples of solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.

[0178] The reaction temperature is preferably 10°C to 100°C, and more preferably 40°C 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.

[0179] 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.

[0180] 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 is not particularly limited as long as it can dissolve the residue of the raw materials, but from the viewpoint of yield, purity, and ease of removal, it is preferable to include at least one selected from the group consisting of 1-hexane, 1-pentane, and cyclohexane.

[0181] The organic solvent used for 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, it is preferable to include at least one selected from the group consisting of ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone, and more preferably to include at least one selected from the group consisting of ethyl acetate, chloroform, toluene, and methyl isobutyl ketone.

[0182] 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.

[0183] (Other hardening agents) The epoxy resin composition of this embodiment may optionally contain other curing agents other than aromatic amine adducts (B-2), compounds represented by formula (3), compounds represented by formula (4), and compounds represented by formula (5). Examples of such other curing agents include amine adducts other than aromatic amine adducts (B-2), amine-imide compounds other than compounds represented by formula (3), compounds represented by formula (4), and compounds represented by formula (5), 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, and thiol-based curing agents.

[0184] Examples of amine-based curing agents include aliphatic amines and aromatic amines.

[0185] Examples of aliphatic amines include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane.

[0186] Examples of aromatic amines include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, 4-aminophenyl-4-aminobenzoate, diethyltoluenediamine, dimethylthiotoluenediamine, diethylthiotoluenediamine, 4,4'-methylenebis[N-(1-methylpropyl)aniline], trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, KAYAHARD(trademark)AA (product name, manufactured by Nippon Kayaku Co., Ltd.), EtaCure 300 (curing agent containing dimethylthiotoluenediamine, manufactured by Mitsui Chemicals Fine, Inc.), and EtaCure 100 Plus (curing agent containing diethyltoluenediamine, manufactured by Mitsui Chemicals Fine, Inc.).

[0187] As the aromatic amine, the above-mentioned aromatic amine compound (B-1) may be used.

[0188] The aromatic amine compound (B-1) preferably includes at least one selected from the group consisting of the aromatic amine compound represented by formula (1) and the compound represented by formula (2). The aromatic amine compound (B-1) may be used alone or in combination of two or more. The above information can be used for the aromatic amine compound (B-1).

[0189] The aromatic amine compound (B-1) preferably contains at least one selected from the group consisting of 4-aminophenyl-4-aminobenzoate (APAB), diethyltoluenediamine, dimethylthiotoluenediamine, diethylthiotoluenediamine, and trimethylenebis(4-aminobenzoate). Diethyltoluenediamine can be at least one selected from the group consisting of 2,4-diamino-3,5-diethyltoluene and 2,6-diamino-3,5-diethyltoluene. When the aromatic amine compound (B-1) contains the above compounds, it tends to exhibit superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0190] Examples of amide-based curing agents include dicyandiamide and its derivatives, such as guanidine compounds, compounds obtained by adding acid anhydrides to amine compounds, and hydrazide compounds.

[0191] Examples of hydrazide compounds include succinate dihydrazide, adipic acid dihydrazide, phthalate dihydrazide, isophthalate dihydrazide, terephthalate dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleate dihydrazide.

[0192] Examples of guanidine compounds include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, and toluylguanidine.

[0193] Examples of phenolic curing agents include phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol cocondensed novolac resin, naphthol-cresol cocondensed novolac resin, and allyl acrylic phenol resin.

[0194] Examples of acid anhydride-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0195] As the active ester compound constituting the active ester-based curing agent, active ester compounds disclosed in Japanese Patent Publication No. 2004-277460 may be used, or commercially available compounds may be used. Examples of commercially available active ester compounds include those containing a dicyclopentadienyldiphenol structure, acetylated phenol novolacs, and benzoylated phenol novolacs. Among these, those containing a dicyclopentadienyldiphenol structure are preferred.

[0196] Examples of products containing a dicyclopentadienyldiphenol structure include EXB9451, EXB9460, EXB9460S, and HPC-8000-65T (hereinafter referred to as trade names, manufactured by DIC Corporation). An example of an acetylated phenol novolac is DC808 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.). An example of a benzoylated phenol novolac is YLH1026 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.).

[0197] Examples of catalytic curing agents include cationic thermosetting catalysts and BF3-amine complexes.

[0198] Examples of microencapsulated latent curing agents include Novacure® HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP, and HXA-9382HP (hereinafter referred to as product names, manufactured by Asahi Kasei Corporation).

[0199] Examples of thiol-based curing agents include 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 1,10-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 polythiols with epoxy compounds.

[0200] If the epoxy resin composition of this embodiment contains other curing agents, their content is preferably 0.01% to 10.0% by mass, more preferably 0.05% to 7.0% by mass, even more preferably 0.1% to 6.0% by mass, and even more preferably 0.3% to 5.0% by mass, based on 100% by mass (total mass) of the resin composition. This tends to improve curability.

[0201] The mass ratio ((X):(Y)) of the total amount (X) of aromatic amine compound (B-1) and aromatic amine adduct (B-2) to the total amount (Y) of the compound represented by formula (3), the compound represented by formula (4), the compound represented by formula (5), and other curing agents is preferably 1:0.05 to 1:10, more preferably 1:0.1 to 1:5, and even more preferably 1:0.2 to 1:3. When the mass ratio is within the above range, the resin composition tends to achieve a better balance between curability and storage stability.

[0202] ((C) Inorganic filler) The epoxy resin composition of this embodiment contains an inorganic filler (C). The inorganic filler (C) is a substance other than silica and does not contain silica. One type of inorganic filler (C) may be used alone, or two or more types may be used in combination.

[0203] In this embodiment, the upper limit of the silica content is usually 100 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less, relative to 100 mass% (total mass) of the inorganic filler (C). The lower limit of the silica content is 0 ppm or more, relative to 100 mass% (total mass) of the inorganic filler (C). It is preferable that the silica content is 0 ppm, relative to 100 mass% (total mass) of the inorganic filler (C).

[0204] The thermal conductivity of the inorganic filler is preferably 2.0 W / m·K or higher, more preferably 10 W / m·K or higher, and even more preferably 20 W / m·K or higher. The upper limit of the thermal conductivity of the inorganic filler is, for example, 2500 W / m·K or lower. When the thermal conductivity of the inorganic filler is within the above range, it tends to have superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0205] In this specification, thermal conductivity can be measured in accordance with ASTM D5470-16 using a thermal conductivity measuring device (for example, SS-H40 (product name), manufactured by Bethel Co., Ltd.).

[0206] The average particle size of the inorganic filler is preferably 0.01 μm to 5 μm, more preferably 0.05 μm to 4 μm, and even more preferably 0.1 μm to 3 μm. Setting the average particle size of the inorganic filler to 0.01 μm or more improves dispersibility in the epoxy resin, reduces the likelihood of thixotropy being imparted to the epoxy resin composition, and tends to improve the flow characteristics of the epoxy resin composition. On the other hand, setting the average particle size of the inorganic filler to 5 μm or less tends to suppress sedimentation of the inorganic filler in the epoxy resin composition, and improves the permeability and fluidity into fine voids of the epoxy resin composition, thereby suppressing the occurrence of voids and unfilled areas. In this specification, the average particle size can be measured, for example, as follows.

[0207] Specifically, the inorganic filler to be measured is added to a solvent (pure water) in an amount of 0.0001% to 5% by mass, along with 1% to 8% by mass of a surfactant. The mixture is then vibrated using an ultrasonic cleaner for 30 seconds to 5 minutes to disperse the inorganic filler. Approximately 3 mL of the dispersion is injected into a measuring cell and measured at 25°C. A laser diffraction particle size analyzer (e.g., LA920 (product name)) is used to measure the volume-based particle size distribution. The average particle size is determined as the particle diameter (D50%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reaches 50%. For example, sodium hexametaphosphate can be used as the surfactant.

[0208] 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. The lower limit of the maximum particle size of the inorganic filler is usually 1 nm or more. The maximum particle size of the inorganic filler can be measured, for example, as follows. The inorganic filler to be measured is added to a solvent (pure water) in an amount of 0.0001% to 5% by mass, along with 1% to 8% by mass of a surfactant. The mixture is then vibrated using an ultrasonic cleaner for 30 seconds to 5 minutes to disperse the inorganic filler. Approximately 3 mL of the dispersion is injected into a measuring cell and measured at 25°C. A laser diffraction particle size analyzer (e.g., LA920 (product name)) is used to measure the volume-based particle size distribution. The average particle size is determined as the particle diameter (D100%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reaches 100%. For example, sodium hexametaphosphate can be used as the surfactant.

[0209] Whether an inorganic filler contains both the first and second particles can be confirmed, for example, by determining the volume-based particle size distribution (frequency distribution) of the inorganic filler. Specifically, if the volume-based frequency distribution of the inorganic filler shows peaks in both the range of 0.2 μm to less than 5 μm and the range of 5 nm to 200 nm, then the inorganic filler can be said to contain both the first and second particles. However, the confirmation method is not limited to the method described above.

[0210] Furthermore, there are no particular limitations on the method for determining the proportion of the first or second particles in the inorganic filler. For example, the particle size distribution (frequency distribution) based on the volume of the inorganic filler can be determined, the peaks corresponding to the first particles and the peaks corresponding to the second particles can be separated at the troughs between them, and the proportion of the first or second particles can be determined by dividing the volume of the particles contained in each separated range by the total volume of the inorganic filler. If the composition of the resin composition is known, the proportion of the first or second particles in the inorganic filler can be determined from the composition of the resin composition. Note that the calculation method is not limited to the above method.

[0211] Furthermore, the particle size distribution of the inorganic filler contained in the resin composition can also be measured by the following method. Specifically, the resin composition containing the inorganic filler is heated at 800°C for 4 hours. After that, the obtained ash is observed with a scanning electron microscope, and particle size distribution data and the average particle size metric (D50%) of the inorganic filler can be obtained by determining the ratio of particle size to number of inorganic fillers from the obtained image.

[0212] Examples of inorganic fillers include powders such as calcium carbonate, clay, alumina (including aluminum oxide), silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, and titania; beads formed from these materials; and glass fibers.

[0213] From the viewpoint of thermal conductivity, the inorganic filler preferably contains at least one selected from the group consisting of alumina, aluminum nitride, boron nitride, and silicon carbide, and more preferably contains alumina.

[0214] Furthermore, from the viewpoint of permeability, the inorganic filler preferably contains at least one selected from the group consisting of aluminum nitride, boron nitride, and silicon carbide, and alumina. The inorganic filler may contain three or more types of fillers.

[0215] Furthermore, the inorganic filler may be surface-treated. Specifically, the inorganic filler may be surface-treated using a silane coupling agent. 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.

[0216] The inorganic filler content is preferably 10.0% to 90.0% by mass, more preferably 68.5% to 90.0% by mass, even more preferably 69.0% to 88.0% by mass, and even more preferably 70.0% to 86.0% by mass, based on 100% by mass (total mass) of the resin composition.

[0217] A inorganic filler content of 68.5% by mass or more tends to easily yield effects of reducing the coefficient of thermal expansion and improving temperature cycling resistance. A inorganic filler content of 90.0% by mass or less tends to suppress the increase in viscosity of the epoxy resin composition, resulting in good fluidity, permeability, and dispensability. In particular, from the viewpoint of improving temperature cycling resistance, a higher lower limit for the inorganic filler content is preferable.

[0218] In this embodiment, even if the inorganic filler content is increased as described above, it is possible to maintain a low viscosity in the resin composition.

[0219] ((D) Silica) The epoxy resin composition of this embodiment preferably further contains silica (D) from the viewpoint of permeability. Examples of silica include fused silica and crystalline silica.

[0220] The thermal conductivity of silica is preferably 0.01 W / m·K or higher, more preferably 0.1 W / m·K or higher, and even more preferably 0.5 W / m·K or higher. The upper limit of the thermal conductivity of silica is, for example, less than 2.0 W / m·K. When the thermal conductivity of silica is within the above range, it tends to have superior penetration and heat dissipation performance in narrow gaps and large areas, as well as superior curability and storage stability.

[0221] The average particle size of silica is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 65 nm or less, and even more preferably 55 nm or less. The lower limit of the average particle size of silica is not particularly limited, but is preferably 5 nm or more. By setting the average particle size of the inorganic filler to 100 nm or less, it tends to be easier to suppress the settling of the inorganic filler in the epoxy resin composition, and the permeability and fluidity into fine gaps of the epoxy resin composition tend to be improved, thereby suppressing the occurrence of voids and unfilled portions.

[0222] Silica may be surface-treated. Specifically, silica may be surface-treated using a silane coupling agent. The silane coupling agent may refer to the silane coupling agents exemplified above in the section on inorganic fillers.

[0223] The silica (D) content is preferably 0.05% to 15.0% by mass, more preferably 0.1% to 10.0% by mass, and even more preferably 0.5% to 7.0% by mass, based on 100% by mass (total mass) of the resin composition.

[0224] A silica content of 0.05% by mass or more tends to easily yield effects of reducing the coefficient of thermal expansion and improving temperature cycling resistance. A silica content of 15.0% by mass or less tends to suppress the increase in viscosity of the epoxy resin composition, resulting in good fluidity, permeability, and dispensability. In particular, from the viewpoint of improving temperature cycling resistance, a higher lower limit for silica content is preferable.

[0225] The mass ratio of inorganic filler (C) to silica (D) (inorganic filler (C):silica (D)) is preferably 99:1 to 80:20, more preferably 98:2 to 85:15, and even more preferably 96:4 to 83:17. A mass ratio of inorganic filler to silica with a lower proportion of inorganic filler than 99:1 tends to improve permeability, while a mass ratio of inorganic filler to silica with a higher proportion of inorganic filler than 80:20 tends to improve thermal conductivity.

[0226] (Other ingredients) The epoxy resin composition of this embodiment may optionally contain other compounding agents different from those listed above, such as curing accelerators, flame retardants, silane coupling agents, mold release agents, and pigments. These can be appropriately selected as long as the effects of this embodiment can be obtained. The flame retardant is not particularly limited, but examples include halides, phosphorus-containing compounds, nitrogen-containing compounds, and inorganic flame retardants.

[0227] The content of other components is typically between 0.01% by mass and 10.0% by mass, based on 100% by mass (total mass) of the resin composition.

[0228] (Epoxy resin composition) The resin composition of this embodiment has a viscosity increase of preferably 1.0 to 10.0 times, more preferably 1.0 to 8.0 times, even more preferably 1.0 to 5.0 times, and even more preferably 1.0 to 3.0 times after being left at 100°C for 60 minutes. This range tends to result in excellent fluidity over a wide area.

[0229] 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 agent (B). The viscosity increase tends to decrease when using aromatic amine adduct (B-2) and, if necessary, curing agents other than aromatic amine adduct (B-2). When using aromatic amine adduct (B-2), the viscosity increase tends to decrease when added to the aromatic amine with an epoxy-based reactive diluent. Furthermore, the viscosity increase also tends to decrease when at least one compound selected from the group consisting of compounds represented by formula (3), formula (4), and formula (5) is used in combination with aromatic amine adduct (B-2). More specifically, for example, the viscosity can be controlled by using an aromatic amine adduct (B-2) containing an ester group and a sulfonyl group in its structure in combination with at least one compound selected from the group consisting of the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5).

[0230] Furthermore, the resin composition of this embodiment preferably has a viscosity of 0.01 Pa·s to 5.5 Pa·s after being left at 100°C for 60 minutes, more preferably 0.01 Pa·s to 4.5 Pa·s, and even more preferably 0.01 Pa·s to 4.0 Pa·s. The viscosity after being left at 100°C for 60 minutes can be measured using a rheometer (e.g., HAAKE® MARS (trade name), manufactured by Thermo Scientific). For specific measurement methods, please refer to the examples.

[0231] The viscosity increase after standing at 100°C for 60 minutes is measured using a rheometer (HAAKE MARS, Thermo Scientific) 5 minutes and 60 minutes after the epoxy resin composition reaches 100°C, by dropping it onto a measurement plate (measurement conditions: aluminum parallel plate, R=35mm, oscillation mode (f=1Hz), shear rate 20 ( / sec)). The viscosity after 5 minutes is defined as "η1," and the viscosity after 60 minutes is defined as "η2." The viscosity increase rate is calculated as η2 / η1. For specific measurement methods, please refer to the examples.

[0232] The epoxy resin composition of this embodiment has a reaction rate of preferably 85% to 100%, more preferably 90% to 100%, even more preferably 92.5% to 100%, and even more preferably 95% to 100% when cured at 165°C. This range results in excellent adhesion and superior package reliability (i.e., less degradation due to temperature and humidity changes).

[0233] The reaction rate can be controlled, for example, by the type of curing agent. Examples of highly reactive curing agents include aromatic amine compounds (B-1), aromatic amine adducts (B-2), compounds represented by formula (3), compounds represented by formula (4), and compounds represented by formula (5). The reaction rate can be controlled to be high by using these, or by combining multiple types of other curing agents, or by increasing the amount added.

[0234] The reaction rate when the resin composition of this embodiment is cured at 165°C can be calculated, for example, by using EXSTER6000 (product name, Hitachi High-Tech Science Co., Ltd.) to raise the temperature from 25°C to 300°C at a rate of 1°C / min and calculating the total amount of heat generated in the temperature range of 100°C to 250°C. The calculation formula is as follows. For specific measurement methods, please refer to the examples. Reaction rate (%) = 100 × (Initial heat generation A - Heat generation after curing B) ÷ Initial heat generation A 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

[0235] <Method for producing resin compositions> The resin composition of this embodiment can be manufactured, for example, by dry blending the components contained in the resin composition of this embodiment, 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 kneading machines.

[0236] The resin composition is preferably obtained, for example, by stirring and mixing each component contained in the resin composition of this embodiment 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.

[0237] Furthermore, it is preferable to prepare the epoxy resin (A) by mixing and stirring beforehand, then disperse the inorganic filler (C) therein to prepare a dispersion, add the curing agent (B) to the dispersion, stir and mix with a rotating / revolving mixer, and then knead with a three-roller mixer. It is preferable to prepare the curing agent (B) by adding an aromatic amine adduct (B-2) and, if necessary, an aromatic amine compound (B-1), then adding the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5), as well as other curing agents, stirring and mixing with a rotating / revolving mixer, and then kneading with a three-roller mixer.

[0238] Furthermore, when silicon carbide is used as the inorganic filler (C), it may damage the three-roll mixer, so it is preferable to mix it using a rotating / revolving mixer, a swivel mixer, or the like.

[0239] <Application> The epoxy resin composition and cured product of this embodiment can be suitably used, for example, as an adhesive, encapsulant, filler, insulating material, sealing material, and prepreg. Examples of adhesives include liquid adhesives, film adhesives, and die bonding materials. Examples of encapsulants include solid encapsulants, liquid encapsulants, and film encapsulants. Examples of liquid encapsulants include underfill materials, potting materials, and dam materials. Examples of insulating materials include insulating adhesive films, insulating adhesive pastes, and solder resists.

[0240] 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.

[0241] ≪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.

[0242] ≪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.

[0243] 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. As a process for manufacturing a semiconductor package using the epoxy resin composition of the present embodiment, a process of manufacturing a semiconductor package may be carried out by appropriately molding the prepared epoxy resin composition and heating it at a predetermined temperature and time to cure it.

Examples

[0244] Hereinafter, the present embodiment will be described with specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. That is, those skilled in the art can implement the present invention by making various changes to the examples shown below. Unless otherwise specified hereinafter, "parts" are based on mass.

[0245] [Evaluation method] (1) Evaluation of high-temperature stability Using the epoxy resin compositions obtained in the following examples and comparative examples, the thickening ratio (η2 / η1) was measured by the following method, and the high-temperature stability was evaluated from the value of the thickening ratio. Using a rheometer (HAAKE (registered trademark) MARS (product name), manufactured by Thermo scientific), at a constant measurement temperature (100 °C), oscillation mode (f = 1 Hz), aluminum parallel plate (R = 35 mm), and shear rate 20 ( / second), a dynamic viscosity η'-temperature curve was obtained when heating the epoxy resin composition (0.6 mL). After the start of measurement, the initial viscosity η1 (100 °C, 5 minutes) was obtained by averaging the viscosity values from 0.95 minutes to 1.05 minutes after the start of measurement within 5 minutes. Also, the viscosity values from 59.95 minutes to 60.05 minutes after the start of measurement were averaged to obtain the viscosity η2 (100 °C, 5 minutes) after storage. The thickening ratio was calculated from the following formula (i). Thickening ratio = viscosity η2 after storage ÷ initial viscosity η1... (i) The measurement time was measured from the time when the epoxy resin composition was dropped onto a hot plate that had reached the flow temperature and the measurement was started 10 seconds after the epoxy resin composition was sandwiched between the measurement plates.

[0246] Using the obtained thickening ratio, the high-temperature stability was evaluated according to the following evaluation criteria. The lower the thickening ratio, the better the stability at high temperatures. 〔Evaluation Criteria〕 A: The thickening ratio was 1.0 times or more and less than 3.0 times. B: The thickening ratio was 3.0 times or more and less than 10.0 times. C: The thickening ratio was 10.0 times or more.

[0247] (2) Evaluation of Penetration The penetration of the epoxy resin compositions obtained in the following examples and comparative examples was evaluated. Two glass plates with two copper foils with a thickness of 25 μm sandwiched at an interval of 10 mm were prepared, and the glass plates were placed on a hot plate and set so that the temperature of the glass plates became 110 °C. Then, the epoxy resin composition taken out from the chamber was dropped into the openings of the two glass plates, and the time required for 20 mm penetration was measured.

[0248] Using the time required for penetration, the penetration was evaluated according to the following evaluation criteria. The shorter the time required for penetration, the better the penetration, and the better the penetration, the better the injectability into a large area. 〔Evaluation Criteria〕 A: The time required for penetration was 0 seconds or more and less than 300 seconds. B: The time required for penetration was 300 seconds or more and less than 350 seconds. C: The time required for penetration was 350 seconds or more and less than 500 seconds. D: The time required for penetration was 500 seconds or more.

[0249] (3) Evaluation of Reactivity The reaction rate when the epoxy resin compositions obtained in the following examples and comparative examples were cured at 165 °C was measured by the following method, and the reactivity was evaluated from the value of the reaction rate. The epoxy resin composition was set in EXSTER6000 (trade name, Hitachi High-Tech Science Corporation), and the temperature was raised from 25 °C to 300 °C at 1 °C / min, and the total amount of heat generation was calculated from the heat generation peak observed in the temperature range from 100 °C to 250 °C. The obtained value was taken as the initial heat generation amount A. Furthermore, the same method was used to measure the amount of heat generated after immersion in a small high-temperature chamber (manufactured by ESPEC) at 165°C for 2 hours. The total amount of heat generated was calculated from the heat-generating peaks observed within the same temperature range. The obtained value was defined as the post-curing heat generation amount B. Using these values, the change in heat generation from the initial state was calculated as a percentage (%) using the following equation (ii), and this was defined as the reaction rate (%). Reaction rate (%) = 100 × (Initial heat generation A - Heat generation B after curing) ÷ Initial heat generation A…(ii) In formula (ii), the initial heat generation A represents the DSC peak heat generation of the resin composition, and the post-curing heat generation B represents the DSC peak heat generation of the resin composition after heating.

[0250] The reaction rate obtained was used to evaluate the reactivity according to the following evaluation criteria. A higher reaction rate indicates superior adhesion and package reliability. [Evaluation Criteria] A: The response rate was between 95% and 100%. B: The response rate was between 90% and 95%. C: The response rate was between 85% and less than 90%. D: The response rate was less than 85%.

[0251] (4) Evaluation of thermal conductivity The epoxy resin compositions obtained in the following examples and comparative examples were cured at 165°C for 2 hours, and the thermal conductivity of the cured products was measured using the method described below. The thermal conductivity was then evaluated from the value of the thermal conductivity. Test specimens were prepared by cutting the cured material into 40mm x 40mm pieces. Subsequently, the thermal conductivity (W / m·k) of the test specimens was measured using a thermal conductivity measuring device (SS-H40 (product name), manufactured by Bethel Co., Ltd.) in accordance with ASTM D5470-16.

[0252] The obtained thermal conductivity was used to evaluate the thermal conductivity according to the following evaluation criteria. Higher thermal conductivity indicates better heat dissipation of the package. [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.

[0253] The abbreviations for each component in the examples and comparative examples are as follows: ((A) Epoxy resin) (A-1) jER(registered trademark)-630LSD (product name, p-aminophenol type epoxy resin, SP value: 22.69, δD: 19.2, δP: 8.8, δH: 8.3, manufactured by Mitsubishi Chemical Corporation) (A-2) jER(registered trademark)-604 (product name, tetraglycidyldiaminodiphenylmethane type epoxy resin, SP value: 22.30, δD: 19.6, δP: 7.3, δH: 7.7, manufactured by Mitsubishi Chemical Corporation)

[0254] ((a) Epoxy-based reactive diluents) (a-1) YED-216 (Trade name, 1,6-Hexanediol diglycidyl ether, SP value: 19.39, δD: 16.90, δP: 7.60, δH: 5.70, Manufactured by Mitsubishi Chemical Corporation) (a-2) EH (ethylhexylglycidyl ether, SP value: 17.36, δD: 16.20, δP: 4.60, δH: 4.20) (a-3) Showfree® CDMDG (trade name, 1,4-cyclohexanedimethanol diglycidyl ether, SP value: 19.75, δD: 17.40, δP: 7.40, δH: 5.70, manufactured by Resonaq Corporation) (a-4) jER(registered trademark)-YX8000D (product name, hydrogenated bisphenol type A epoxy resin, SP value: 18.76, δD: 17.40, δP: 5.70, δH: 4.10, manufactured by Mitsubishi Chemical Corporation) (a-5) DYBP (DY-BP (product name), n-butylglycidyl ether, SP value: 18.31, δD: 16.40, δP: 6.00, δH: 5.50, manufactured by Yokkaichi Synthetic Co., Ltd.) ·EGE (2-ethylglycidyl ether, SP value: 19.00, δD: 16.40, δP: 7.30, δH: 6.20) ·PEGDGE: polyethylene glycol diglycidyl ether (Denacol (registered trademark) EX830 (trade name), SP value: 20.07, δD: 16.40, δP: 7.50, δH: 8.80)

[0255] ((B) Curing agent) (B-1A) DETDA: Ethacure 100 Plus (+): Curing agent containing diethyltoluenediamine (manufactured by Mitsui Chemicals Fine Co., Ltd.) (B-1B) DMTDA: Ethacure 300: Curing agent containing dimethylthiotoluenediamine (manufactured by Mitsui Chemicals Fine Co., Ltd.) (B-1C) MBDA: 4,4'-methylenebis[N-(1-methylpropyl)aniline] (Kumiai Chemical Industry Co., Ltd.) ·APAB: 4-aminophenyl-4-aminobenzoate

[0256] <Preparation of curing agent> (Synthesis of compound (B-2A)) After purging a 500 ml four-necked flask equipped with a reflux tube and a stirring blade with nitrogen, 20 g of 1-butanol and 0.05 mol of Ethacure 100 Plus (+) (DETDA) were added, and the mixture was heated until the internal temperature reached 120°C. Then, using a dropping funnel, 0.05 mol of ethylhexyl glycidyl ether (EH) was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction solution was stirred while heating at 120°C for 6 hours to complete the reaction. From the obtained solution, 1-butanol was distilled off 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) (DETDA adduct-2-EH).

[0257] (Synthesis of compound (B-2B)) Compound (B-2B) (DETDA adduct-DYBP) was obtained in the same manner as the synthesis of compound (B-2A) above, except that 2-EH was changed to n-butyl glycidyl ether (DYBP).

[0258] (Synthesis of compound (B-2C)) Compound (B-2C) (DETDA adduct-EGE) was obtained by the same method as the synthesis of compound (B-2A) above, except that 2-EH was replaced with 2-ethylglycidyl ether (EGE).

[0259] (Synthesis of compound (B-2D)) Compound (B-2D) (APAB adduct-2-EH) was obtained by following the same procedure as the synthesis of compound (B-2A) above, except that EtaCure 100 Plus (+) (DETDA) was replaced with 4-aminophenyl-4-aminobenzoate (APAB).

[0260] (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 (PEGDGE) were weighed into a round-bottom flask, and the flask was heated in an oil bath until it reached 90°C. Next, 1.62 g (0.016 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After the addition was complete, the mixture was stirred and allowed to react for 4 hours at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted starting materials by distillation, yielding the liquid product compound (B-3A). According to the infrared absorption spectrum measurement method, the IR(KBr) is 1570 cm⁻¹. -1 The following measurements were obtained. Mass spectrometry revealed a peak at m / z = 839.6. This confirmed that the compound (B-3A) shown in the following formula was obtained.

[0261] [ka]

[0262] (Synthesis of compound (B-3B)) 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of n-butyl glycidyl ether (DYBP) 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 and allowed to react for 4 hours at 90°C to complete the reaction. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted starting materials by distillation, yielding the liquid product compound (B-3B). According to the infrared absorption spectrum measurement method, the IR(KBr) is 1570 cm⁻¹. -1 The following measurements were obtained. Mass spectrometry revealed a peak at m / z = 287.2. This confirmed that the compound (B-3B) shown in the following formula was obtained.

[0263] [ka]

[0264] (Synthesis of compound (B-3C)) A solution was obtained by mixing 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 ethylhexyl glycidyl ether (EH), and 21.67 g (0.29 mol) of t-butyl alcohol. This solution was reacted at 55°C for 4 days with stirring to obtain a reaction mixture. The resulting reaction mixture was concentrated under reduced pressure at 55°C to remove t-butyl alcohol, by-product alcohol, and unreacted starting materials by distillation, thereby obtaining a solid product. The product was dissolved in ethyl acetate and washed repeatedly with water using a separatory funnel to remove unreacted starting material residue. This organic layer was concentrated again under reduced pressure at 55°C to obtain 33.05 g (84.1% yield) of compound (B-3C), which is a white, amorphous solid. According to the infrared absorption spectrum measurement method, the IR(KBr) is 1570 cm⁻¹. -1The following measurements were obtained. Mass spectrometry revealed a peak at m / z = 655.8. This confirmed that the compound (B-3C) shown in the following formula was obtained.

[0265] [ka]

[0266] (Synthesis of compound (B-3D)) A solution was obtained by mixing 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). This solution was reacted at 90°C for 4 hours with stirring to obtain a reaction mixture. The resulting reaction mixture was concentrated under reduced pressure at 80°C to remove by-product alcohol and unreacted starting materials, thereby obtaining a liquid amineimide compound (B-3D). According to the infrared absorption spectrum measurement method, the IR(KBr) is 1570 cm⁻¹. -1 The following measurements were obtained. Mass spectrometry revealed a peak at m / z = 705.4. This confirmed that the compound (B-3D) shown in the following equation was obtained.

[0267] [ka]

[0268] ((C) Inorganic filler) (C-1A) Epoxy surface-treated alumina: Alumina obtained by surface treatment with 3-glycidoxypropyltrimethoxysilane (thermal conductivity: 30 (W / m·K), average particle size: 0.25 μm) (C-1B) Amino-surface treated alumina: Alumina obtained by surface treatment with N-phenyl-3-aminopropyltrimethoxysilane (thermal conductivity: 30 (W / m·K), average particle size: 0.25 μm)

[0269] <Preparation of inorganic fillers> (Inorganic filler (C-1C)) 100 g of alumina (average particle size 0.9 μm) and 3 g of 3-glycidoxypropyltrimethoxysilane were mixed using a stirrer at room temperature for 10 minutes and stirred. Afterward, the mixture was aged for 24 hours to obtain an inorganic filler (C-1C) (epoxy surface-treated alumina, average particle size 0.9 μm). The thermal conductivity of the epoxy surface-treated alumina was 30 (W / m·K).

[0270] (Inorganic filler (C-1D)) Inorganic filler (C-1D) (epoxy surface-treated alumina with an average particle size of 0.4 μm) was prepared using the same method as for inorganic filler (C-1C) described above, except that alumina (average particle size 0.9 μm) was replaced with alumina (average particle size 0.4 μm). The thermal conductivity of the epoxy surface-treated alumina was 30 (W / m·K).

[0271] (C-2A) Aluminum nitride filler (average particle size: 0.9 μm, thermal conductivity: 200 (W / m·K)) (C-3A) Silicon carbide filler (average particle size: 1.2 μm, thermal conductivity: 270 (W / m·K)) (C-4A) Boron nitride filler (average particle size: 1.4 μm, thermal conductivity: 80 (W / m·K))

[0272] (D) Silica (D-1) Spherical silica (average particle size: 0.05 μm, thermal conductivity: 1.9 (W / m·K))

[0273] (Examples 1-21 and Comparative Example 1) Each component listed in Tables 1 and 2 was placed in the proportions specified in Tables 1 and 2 in a plastic stirring container. This mixture was then stirred and mixed using a rotating / revolving mixer (Sinky Co., Ltd. "ARE-310" (product name)), and finally kneaded with a three-roll mill to prepare the epoxy resin composition. In the examples and comparative examples, epoxy resin (A) was prepared by mixing and stirring beforehand, and inorganic filler (C) was dispersed therein to prepare a dispersion. Then, curing agent (B) was added to the dispersion and stirred and mixed in a rotary / revolving mixer. After that, the epoxy resin composition was prepared by kneading with a three-roller mixer. In addition, for curing agent (B), compounds (B-2A) to (B-2D) and compounds (B-3A) to (B-3D) were added as appropriate, then compounds (B-1A) to (B-1C) were added as appropriate, and then stirred and mixed in a rotary / revolving mixer, and then kneaded with a three-roller mixer.

[0274] Each of the resulting epoxy resin compositions was poured into a Teflon (registered trademark) mold and heated at 165°C for 2 hours to produce a cured product. Tables 1 and 2 show the evaluation results of the resin compositions and cured products obtained in Examples 1 to 21 and Comparative Example 1.

[0275] [Table 1]

[0276] [Table 2]

[0277] As shown in Tables 1 and 2, the epoxy resin composition of this embodiment exhibited excellent curability and storage stability, as well as good penetration and heat dissipation performance in narrow gaps and large areas. On the other hand, Comparative Example 1, which did not contain aromatic amine adduct (B-2), exhibited poor curability and storage stability, as well as poor penetration and heat dissipation performance in narrow gaps and large areas.

Claims

1. An epoxy resin composition comprising an epoxy resin (A), a curing agent (B), and an inorganic filler (C), The curing agent (B) comprises a reactive compound having a functional group capable of reacting with the aromatic amine compound (B-1), and an aromatic amine adduct (B-2) which is a reaction product of the aromatic amine compound (B-1). The inorganic filler (C) is something other than silica. Epoxy resin composition.

2. The epoxy resin composition according to claim 1, wherein the thermal conductivity of the inorganic filler (C) is 2.0 W / m·K or higher.

3. The epoxy resin composition according to claim 1, wherein the aromatic amine compound (B-1) comprises at least one selected from the group consisting of aromatic amine compounds represented by the following formula (1) and aromatic amine compounds represented by the following formula (2). 【Chemistry 1】 (In formula (1), R α and R β Each of the following independently represents a monovalent organic group or halogen with 1 to 20 carbon atoms, a and b are each independently integers from 0 to 4, and X represents a divalent organic group or single bond. 【Chemistry 2】 (In formula (2), R γ Each of these independently represents a monovalent organic group or halogen with 1 to 20 carbon atoms, where c is an integer from 1 to 4.

4. The epoxy resin composition according to claim 1, wherein the reactive compound is an epoxy compound having one glycidyl group in its molecule.

5. The epoxy resin composition according to claim 1, wherein the content of the aromatic amine adduct (B-2) is 0.1% by mass or more and 10.0% by mass or less, based on 100% by mass of the resin composition.

6. The epoxy resin composition according to claim 1, wherein the curing agent (B) further comprises at least one selected from the group consisting of a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5). 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (In formulas (3) to (5), R 1 each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxy group, a carbonyl group, an ester bond or an ether bond; R 2 and R 3 each independently represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an aryl group or an aralkyl group, or they are linked to form a heterocyclic ring having 7 or less carbon atoms; R 4 each independently represents a hydrogen atom or an n-valent organic group having 1 to 60 carbon atoms which may contain an oxygen atom; n represents 2 or 3. R 5 represents a nitrogen atom having a negative charge, and R 6 and R 6 represents a nitrogen atom having a positive charge.).

7. The epoxy resin composition according to claim 6, wherein the total content of the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) is 0.1% by mass or more and 10.0% by mass or less, based on 100% by mass of the resin composition.

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

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

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

11. The epoxy resin composition according to claim 1, wherein the content of the inorganic filler (C) is 10.0% by mass or more and 90.0% by mass or less, based on 100% by mass of the resin composition.

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

13. The silica (D) content is 0.05% by mass or more and 15.0% by mass or less, based on 100% by mass of the resin composition. The epoxy resin composition according to claim 12, wherein the mass ratio of the inorganic filler (C) to the silica (D) (inorganic filler (C): silica (D)) is 99:1 to 80:

20.

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

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

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

17. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) comprises an epoxy resin having a solubility parameter (SP value) of 15.0 or more and 21.0 or less.

18. The epoxy resin composition according to claim 1, wherein the content of the epoxy resin (A) is 5.0% by mass or more and 15.0% by mass or less, based on 100% by mass of the resin composition.

19. The epoxy resin composition according to claim 1, further comprising an epoxy-based reactive diluent (a).

20. The epoxy resin composition according to claim 19, wherein the epoxy-based reactive diluent (a) comprises an epoxy-based reactive diluent having a solubility parameter (SP value) of 15.0 or more and 21.0 or less.

21. The epoxy resin composition according to claim 19, wherein the content of the epoxy-based reactive diluent (a) is 1.0% by mass or more and 10.0% by mass or less based on 100% by mass of the resin composition.

22. The epoxy resin composition according to claim 1, wherein the viscosity increase rate after being left at 100°C for 60 minutes is 1.0 times or more and 10.0 times or less.

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

24. A cured product comprising the epoxy resin composition according to any one of claims 1 to 23.

25. A sealing material comprising the cured product described in claim 24.

26. The encapsulant according to claim 25, which is for use in semiconductors.

27. An adhesive comprising the epoxy resin composition according to any one of claims 1 to 23.

28. A semiconductor package comprising the cured product described in claim 24.

29. 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 23.

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