Curing agent for epoxy resins, epoxy resin composition, cured object, sealing material, and adhesive

Abstract

Provided is a curing agent for epoxy resins which comprises an aromatic amine compound represented by formula (1), (2), or (3) and an aromatic amine adduct that is a product of reaction between an aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound. Rα and Rβ2 in formula (1), Rγ and Rδ in formula (2), and Rε in formula (3) each independently represent a C1-C20 monovalent organic group or a halogen atom; a and b are each independently an integer of 0-4; X represents a divalent organic group having one or more aromatic rings or represents -O-, -CO-, -C(=O)O-, -SO2-, or -C(=O)NH-; c and d are each independently an integer of 1-4; Y represents a divalent organic group or a single bond; and e is an integer of 1-4.

Description

Epoxy resin curing agents, epoxy resin compositions, cured products, sealing materials and adhesives

[0001] The present invention relates to a curing agent for epoxy resins, an epoxy resin composition, a cured product, a sealing material, and an adhesive.

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

[0003] Patent Document 1 describes an epoxy resin represented by a specific general formula.

[0004] Patent Document 2 describes an epoxy resin composition comprising (A) an epoxy resin, (B) an aromatic amine-based curing agent, (C) a curing accelerator, and (D) a stabilizer, wherein the ratio of the equivalents of all amino groups in the aromatic amine-based curing agent (B) to 1 equivalent of all epoxy groups in the epoxy resin (A) is 0.7 to 1.5, the curing accelerator (C) is an organic boron compound selected from aryl borate salts or aryl borane complexes, and the stabilizer (D) is an aryl phosphine.

[0005] Japanese Patent No. 6282515 Japanese Patent Application Laid-Open No. 2019-172738

[0006] Currently, commonly used epoxy resin compositions include so-called two-component epoxy resin compositions in which an epoxy resin and a curing agent are mixed at the time of use.

[0007] Although two-component epoxy resin compositions can be cured at room temperature, the epoxy resin and curing agent must be stored separately and then measured and mixed as needed before use. This makes storage and handling cumbersome. Furthermore, since the usable time is limited, it is not possible to premix a large amount of the components, which increases the mixing frequency and inevitably reduces efficiency.

[0008] To solve these problems associated with two-component epoxy resin compositions, several one-component epoxy resin compositions have been proposed, including, for example, epoxy resin compositions in which an epoxy resin curing agent is blended with an epoxy resin.

[0009] Recently, there are a wide variety of demands for electronic devices. These demands include, for example, miniaturization, high functionality, light weight, high performance, and multifunctionality. More specifically, for example, in semiconductor chip mounting technology, there is a demand for finer electrode pads and finer pad pitches, resulting in further miniaturization, miniaturization, and higher density. Furthermore, underfills are used as adhesives to be placed in the gap between a chip and a substrate for purposes such as protecting bump connections and the circuit surface of the chip. To meet the demand for increasingly finer pitches, underfills that can penetrate narrower gaps are required. Furthermore, in recent years, there has been a growing demand not only for finer pitches but also for larger semiconductor chips, potentially increasing the penetration time of underfills. Therefore, underfills are also required to exhibit minimal change in viscosity during penetration at high temperatures and during storage.

[0010] As described above, the latent curing agent constituting the one-component epoxy resin composition is required to have both good curability after mixing with the epoxy resin and good storage stability, as well as good permeability into minute regions such as between densely packed fibers such as carbon fibers and glass fibers, and narrow gaps in electronic components.

[0011] In the above Patent Document 1, the curing agent used is solid, and there is room for improvement in terms of penetration into narrow gaps.

[0012] The above-mentioned Patent Document 2 requires a step of adding an additive to improve the storage stability and adhesiveness of the curing agent, and there is room for improvement in terms of storage and handling.

[0013] The problem to be solved by the present invention is to provide an epoxy resin curing agent that has excellent permeability after being mixed with an epoxy resin and is capable of achieving both curability and storage stability, and an epoxy resin composition, a cured product, a sealant, and an adhesive that each contain the epoxy resin curing agent.

[0014] This embodiment includes the following aspects: <1> A curing agent for epoxy resins, comprising: an aromatic amine compound (A-1) represented by the following formula (1), (2), or (3); and an aromatic amine adduct (A-2) that is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).

[0015]

[0016] In formula (1), R α and R β each independently represents 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; X represents a divalent organic group having one or more aromatic rings, or -O-, -CO-, -C(=O)O-, -SO ２ - or -C(=O)NH-.

[0017]

[0018] In formula (2), R γ and R δ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; c and d each independently represent an integer of 1 to 4; and Y represents a divalent organic group or a single bond.

[0019]

[0020] In formula (3), R εrepresents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and e is an integer of 1 to 4. <2> The epoxy resin curing agent according to <1>, which has a glass transition temperature (Tg) of 10°C or lower as detected by differential scanning calorimetry (DSC) at a heating rate of 5°C / min. <3> The epoxy resin curing agent according to <1> or <2>, which has at least one melting point (Tm) of 60°C or lower as detected by differential scanning calorimetry (DSC) at a heating rate of 5°C / min. <4> An epoxy resin curing agent comprising: an aromatic amine compound (A-1); and an aromatic amine adduct (A-2) which is a reaction product of the aromatic amine compound and a reactive compound having a functional group reactive with the aromatic amine compound, wherein the glass transition temperature (Tg) of the epoxy resin curing agent according to <1>, which has a glass transition temperature (Tg) of 20°C or lower as detected by differential scanning calorimetry (DSC) at a heating rate of 5°C / min. <5> The epoxy resin curing agent according to <4>, which has a glass transition temperature (Tg) of 5° C. or lower as detected by differential scanning calorimetry (DSC) at a heating rate of 5° C. / min. <6> The epoxy resin curing agent according to <4> or <5>, which has a glass transition temperature (Tg) of −20° C. or lower as detected by differential scanning calorimetry (DSC) at a heating rate of 5° C. / min. <7> The epoxy resin curing agent according to any one of <4> to <6>, wherein the aromatic amine compound (A-1) is an aromatic amine compound represented by the following formula (11) or (12):

[0021]

[0022] In formula (11), R α and R β each independently represents 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.

[0023]

[0024] In formula (12), R γrepresents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and c is an integer of 1 to 4. <8> The epoxy resin curing agent according to any one of <1> to <7>, which has no detectable melting point (Tm) in the range of -20°C to 60°C in differential scanning calorimetry (DSC) measured at a heating rate of 5°C / min in the temperature range of -50°C to 200°C. <9> The epoxy resin curing agent according to any one of <1> to <8>, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1), obtained by liquid chromatography analysis (UV detector), is 0.10 to 0.45. <10> The epoxy resin curing agent according to any one of <1> to <8>, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.5 to 2.0. <11> The epoxy resin curing agent according to any one of <1> to <10>, wherein the reactive compound is a compound having one glycidyl group in the molecule. <12> An epoxy resin composition comprising the epoxy resin curing agent according to any one of <1> to <11>, an epoxy resin (B), and an inorganic filler (C). <13> The epoxy resin composition according to <12>, further comprising a curing accelerator (D). <14> The epoxy resin composition according to <13>, wherein the curing accelerator (D) is at least one selected from the group consisting of a compound (D-1) represented by the following formula (4), the following formula (5), or the following formula (6), and an imidazole-based compound (D-2):

[0025]

[0026]

[0027]

[0028] (In formulas (4) to (6), R １ each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. ５ represents a negatively charged nitrogen atom, R ６ represents a positively charged nitrogen atom.) <15> The epoxy resin composition according to any one of <12> to <14>, wherein the content of the inorganic filler (C) is 40% by mass to 70% by mass relative to the total amount of the epoxy resin composition. <16> The epoxy resin composition according to any one of <12> to <15>, wherein the viscosity (η2) after standing at 110°C for 60 minutes is 0.01 Pa s to 1.50 Pa s. <17> The epoxy resin composition according to <16>, wherein the ratio (thickness increase rate, η2 / η1) of the viscosity (η2) after standing at 110°C for 60 minutes to the viscosity (η1) after standing at 110°C for 5 minutes is 1.0 to 40.0 times, and wherein the reaction rate when cured at 165°C is 80% to 99%. <18> The epoxy resin composition according to any one of <12> to <17>, which has a viscosity of 50 Pa s or less at 25°C. <19> A cured product of the epoxy resin composition according to any one of <12> to <18>. <20> An encapsulant comprising the cured product according to <19>. <21> The encapsulant according to <20>, which is an encapsulant for semiconductors. <22> An adhesive comprising the epoxy resin composition according to any one of <12> to <18>. <23> A semiconductor package comprising the cured product according to <19>. <24> A method for producing a semiconductor package, which comprises a step of producing a semiconductor package using the epoxy resin composition according to <12>.

[0029] According to the present invention, there can be provided an epoxy resin curing agent that, after being mixed with an epoxy resin, has excellent permeability and is capable of achieving both curability and storage stability, as well as an epoxy resin composition, a cured product, a sealant, and an adhesive each containing the epoxy resin curing agent.

[0030] Hereinafter, a detailed description will be given of an embodiment of the present invention (hereinafter simply referred to as "the present embodiment"). The following embodiment is an example for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented by appropriate modifications within the scope of the gist thereof. In this specification, when a numerical value or physical property value is enclosed before and after "~", the preceding and following values ​​are included. In the numerical ranges described in this specification in stages, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with a value shown in the Examples. In the description of groups (atomic groups) in this specification, a notation that does not specify whether they are substituted or unsubstituted includes both unsubstituted and substituted groups. For example, the term "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0031] This embodiment includes the following first and second embodiments.

[0032] [First embodiment] <Epoxy resin curing agent> The epoxy resin curing agent of the first embodiment includes an aromatic amine compound (A-1) represented by the following formula (1), (2), or (3), and an aromatic amine adduct (A-2) that is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).

[0033]

[0034] In formula (1), R α and R βeach independently represents 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; X represents a divalent organic group having one or more aromatic rings, or -O-, -CO-, -C(=O)O-, -SO ２ - or -C(=O)NH-.

[0035]

[0036] In formula (2), R γ and R δ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; c and d each independently represent an integer of 1 to 4; and Y represents a divalent organic group or a single bond.

[0037]

[0038] In formula (3), R ε represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.

[0039] The epoxy resin curing agent of the first embodiment contains the above-described components, and therefore after being mixed with an epoxy resin, can have excellent permeability and can achieve both curability and storage stability.

[0040] <Aromatic Amine Compound (A-1)> The aromatic amine compound (A-1) is represented by formula (1), the following formula (2), or the following formula (3).

[0041]

[0042] In formula (1), R α and R β each independently represents 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; X represents a divalent organic group having one or more aromatic rings, or -O-, -CO-, -C(=O)O-, -SO ２X represents -, or -C(=O)NH-. More preferably, X represents a divalent organic group having one or more aromatic rings, or -O-, -CO-, -C(=O)O-, or -C(=O)NH-. This reduces the reactivity and compatibility with the epoxy resin, resulting in poor curability despite excellent viscosity stability, and it is possible to prevent a decrease in Tg.

[0043] R α and R βIn the above formula, the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. a and b are each independently an integer of 0 to 2, and more preferably 0 or 1. In X, the divalent organic group having one or more aromatic rings preferably has one aromatic ring, and more preferably has one benzene ring. Examples of the aromatic amine compound represented by formula (1) include 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-4-aminobenzoate, 2-fluoro-4-aminophenyl-4-aminobenzoate, 3-fluoro-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-3-methyl-4-aminobenzoate, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, and 1,3-bis(3-aminophenoxy). Examples of suitable amines include benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, and 1,4-bis(3-aminopropyldimethylsilyl)benzene. It is preferable to use at least one selected from the group consisting of these amines.Among the above, from the viewpoint of achieving both curability and storage stability after mixing with an epoxy resin, the aromatic amine compound represented by formula (1) preferably has —O—, —CO—, —C(═O)O— or —C(═O)NH— as X, more preferably has a —CO—, —C(═O)O— or —C(═O)NH— bond, and more preferably has a —C(═O)O- bond.

[0044]

[0045] In formula (2), R γ and R δ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; c and d each independently represent an integer of 1 to 4; and Y represents a divalent organic group or a single bond.

[0046] R γ and R δ In the formula (2), the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. c and d are each independently preferably an integer of 0 to 2, more preferably 0 or 1. The aromatic amine compound represented by formula (2) is a compound other than the aromatic amine compound represented by formula (1). Therefore, in Y of formula (2), the divalent organic group may be a divalent organic group having no aromatic ring.

[0047] Examples of aromatic amine compounds represented by formula (2) 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, and it is preferable to use one or more selected from the group consisting of these. Among the above, 3,3'-diethyl-4,4'-diaminodiphenylmethane is more preferred as the aromatic amine compound represented by formula (2) from the viewpoint of achieving both curability and storage stability after mixing with an epoxy resin.

[0048]

[0049] In formula (3), R ε represents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and e is an integer of 1 to 4. ε In the formula (I), the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and even more preferably has 1 to 3 carbon atoms. e is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0050] Examples of the aromatic amine compound represented by formula (3) include diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, etc., and it is preferable to use one or more selected from the group consisting of these. Among these, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene and 2,6-diamino-3,5-diethyltoluene) is preferred as the aromatic amine compound represented by formula (3) from the viewpoint of achieving both curability and storage stability after mixing with an epoxy resin.

[0051] <Aromatic Amine Adduct (A-2)> The aromatic amine adduct (A-2) is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).

[0052] (Reactive Compound) The reactive compound has a functional group capable of reacting with the aromatic amine compound (A-1). Examples of the functional group include a —C(═O)OC(═O)— group, a carboxyl group, a sulfo group, an isocyanato group, a carbonyl group, an epoxy group, a fluoro group, a chloro group, a bromo group, and an iodo group.

[0053] The reactive compound is preferably at least one compound selected from the group consisting of acid anhydrides, acid dianhydrides, carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, epoxy compounds, and alkyl halide compounds.

[0054] Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

[0055] Examples of sulfonic acid compounds include ethanesulfonic acid and p-toluenesulfonic acid.

[0056] Examples of isocyanate compounds include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates. Examples of aliphatic diisocyanates include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of alicyclic diisocyanates include isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, and 1,3-bis(2-isocyanatopropyl-2-yl)-cyclohexane. Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of aliphatic triisocyanates include 1,3,6-triisocyanatomethylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl. Examples of polyisocyanates include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above diisocyanate compounds. Examples of polyisocyanates derived from the above diisocyanates include isocyanurate-type polyisocyanates, biuret-type polyisocyanates, urethane-type polyisocyanates, allophanate-type polyisocyanates, and carbodiimide-type polyisocyanates. Examples of urea compounds include urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.

[0057] The epoxy compound may be a monoepoxy compound, a polyepoxy compound, or a mixture thereof. Examples of the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.Examples of polyfunctional 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 dihydric 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; and epoxy compounds obtained by glycidylating tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. compounds; novolac-type epoxy compounds obtained by glycidylating novolacs such as phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and brominated bisphenol A novolac; aliphatic ether-type epoxy compounds obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol; ether ester-type epoxy compounds obtained by glycidylating hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid; ester-type epoxy compounds obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl-type epoxy compounds such as epoxy compounds obtained by glycidylating amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and epoxy compounds obtained by glycidylating amine-type epoxy compounds such as triglycidyl isocyanurate; and alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate.

[0058] Among the above, from the viewpoint of excellent curability and storage stability, the reactive compound is preferably an epoxy compound, and more preferably an epoxy compound having one glycidyl group in the molecule.

[0059] In order to achieve both high curability and storage stability, the total chlorine content of the epoxy compound is preferably 400 ppm or less. It is 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 preferably 80 ppm or less, and even more preferably 50 ppm or less. In the first embodiment, the total chlorine content refers to the total amount of organic chlorine and inorganic chlorine contained in the compound, and is a value based on the mass of the compound. Of the total chlorine, the chlorine contained in 1,2-chlorohydrin groups is generally referred to as hydrolyzable chlorine. The amount of hydrolyzable chlorine in the epoxy compound used in the first embodiment is preferably 50 ppm or less, more preferably 0.01 to 20 ppm, and even more preferably 0.05 to 10 ppm. A hydrolyzable chlorine content of 50 ppm or less is advantageous for achieving both high curability and storage stability, and is preferred because it exhibits excellent electrical properties. In the first embodiment, when it is desired to reduce the total chlorine content of an epoxy compound, examples thereof include a method in which a dechlorination reaction is carried out using a base catalyst in an aprotic solvent and then the epoxy compound is purified by washing with water, and a method in which a dechlorination reaction is carried out using a metal amide compound such as a bis(trialkylsilyl)amide metal salt as a catalyst and then the epoxy compound is purified by washing with water.

[0060] The aromatic amine adduct (A-2) is a reaction product of an aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1). The aromatic amine adduct (A-2) used in the first embodiment can be obtained, for example, by reacting 1 to 5 moles of the aromatic amine compound (A-1) with 1 to 5 moles of a reactive compound (e.g., an epoxy compound) in the presence of a solvent, for example, at a temperature of 50 to 250°C for 0.1 to 24 hours, and then removing the unreacted aromatic amine compound (A-1) and the solvent, as necessary. The solvent used here is not particularly limited, but examples thereof include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, etc.; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, etc.; water, etc., and these solvents may be used in combination. Furthermore, when an aromatic amine compound (A-1) that is liquid at room temperature is used, no solvent may be used.

[0061] <Glass Transition Temperature (Tg)> The epoxy resin curing agent of the first embodiment preferably has a glass transition temperature (Tg) of 10°C or less, as detected by differential scanning calorimetry (DSC analysis) measured at a temperature rise rate of 5°C / min. A Tg of 10°C or less can suppress viscosity changes in high-temperature environments during penetration and during storage, resulting in excellent penetration properties. From the above viewpoints, the Tg is more preferably 10°C or less, even more preferably 5°C or less, and particularly preferably 0°C or less. On the other hand, from the viewpoint of suppressing viscosity changes, the Tg is preferably -50°C or more, more preferably -45°C or more, and even more preferably -40°C or more.

[0062] The glass transition temperature (Tg) of an epoxy resin curing agent is measured by the following method. Using a differential scanning calorimeter (for example, a differential scanning calorimeter system "DSC Q2000" manufactured by TA Instruments-Waters), a 10 mg sample is heated from -50°C to 200°C at a heating rate of 5°C / min under a nitrogen gas flow (40 mL / min). The Tg of the epoxy resin curing agent is the peak top temperature of the DSC differential curve (JIS K6240:2011).

[0063] The epoxy resin curing agent of the first embodiment preferably has at least one melting point (Tm) of 60°C or less as detected by differential scanning calorimetry (DSC analysis) measured at a temperature rise rate of 5°C / min. A Tm of 60°C or less can suppress viscosity changes in high-temperature environments during penetration and during storage, resulting in excellent penetration properties. From the above viewpoints, Tm is more preferably 60°C or less, even more preferably 50°C or less, and particularly preferably 40°C or less. On the other hand, from the viewpoint of excellent curing properties, Tm is preferably -40°C or more, more preferably -20°C or more, and even more preferably -10°C or more.

[0064] It is also preferable that the epoxy resin curing agent of the first embodiment has no detectable melting point (Tm) in the range of -20°C to 60°C in differential scanning calorimetry (DSC analysis) measured at a temperature rise rate of 5°C / min in the temperature range of -50°C to 200°C. The aromatic amine compound represented by formula (2) or (3) exhibits amorphousness due to the inhibition of intermolecular interactions caused by the inclusion of a substituent on the side chain. In other words, since no detectable melting point (Tm) is detected in the range of -20°C to 60°C, the compound has excellent viscosity at the temperature during penetration and excellent penetration properties.

[0065] The melting point (Tm) of an epoxy resin curing agent is measured by the following method. Using a differential scanning calorimeter (for example, a differential scanning calorimeter system "DSC Q2000" manufactured by TA Instruments-Waters), a 10 mg sample is heated from -50°C to 200°C at a heating rate of 5°C / min under a nitrogen gas flow (40 mL / min). The Tm of an epoxy resin curing agent is the apex temperature of the endothermic peak in the DSC curve (JIS K7121:1987).

[0066] In the epoxy resin curing agent of the first embodiment, the aromatic amine adduct (A-2) may include an aromatic amine adduct (A-2-1) in which one molecule of a reactive compound is added to one molecule of an aromatic amine compound (A-1), and an aromatic amine adduct (A-2-2X) in which two or more molecules of a reactive compound are added to one molecule of an aromatic amine compound (A-1).

[0067] In the epoxy resin curing agent of the first embodiment, the aromatic amine adduct (A-2) preferably includes an aromatic amine adduct (A-2-1) in which one molecule of a reactive compound is added to one molecule of the aromatic amine compound (A-1). Furthermore, the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1), as determined by liquid chromatography analysis (UV detector), is preferably 0.10 to 0.45. Having (A-1 / A-2-1) of 0.10 or greater provides superior curability. From the above perspective, (A-1 / A-2-1) is more preferably 0.10 or greater, even more preferably 0.12 or greater, and particularly preferably 0.15 or greater. On the other hand, having (A-1 / A-2-1) of 0.45 or less provides superior penetration. From the above viewpoints, (A-1 / A-2-1) is more preferably 0.45 or less, even more preferably 0.42 or less, and particularly preferably 0.40 or less. Therefore, by making (A-1 / A-2-1) 0.10 to 0.45, both curability and excellent penetration can be achieved.

[0068] In the epoxy resin curing agent of the first embodiment, the aromatic amine adduct (A-2) preferably includes an aromatic amine adduct (A-2-1) in which one molecule of a reactive compound is added to one molecule of the aromatic amine compound (A-1). Furthermore, the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1), as determined by liquid chromatography analysis (UV detector), is preferably 0.50 to 2.00. Having an (A-1 / A-2-1) ratio of 0.50 or greater provides excellent heat resistance when cured with an epoxy resin. From the above perspectives, (A-1 / A-2-1) is more preferably 0.5 or greater, even more preferably 0.75 or greater, and particularly preferably 1.2 or greater. On the other hand, having an (A-1 / A-2-1) ratio of 2.0 or less provides excellent permeability and storage stability. From the above viewpoints, (A-1 / A-2-1) is more preferably 2.0 or less, even more preferably 1.9 or less, and particularly preferably 1.8 or less. Therefore, by making (A-1 / A-2-1) 0.50 to 2.00, excellent heat resistance can be obtained when cured with an epoxy resin, and both penetration and storage stability can be achieved.

[0069] [Analysis of Components in Epoxy Resin Curing Agent] The method for analyzing each component in the epoxy resin curing agent is as follows. After adjusting the concentration of the amine adduct synthesized in the Synthesis Example to 10% by mass with THF, a 1 mg / mL acetonitrile solution was prepared and subjected to LC / MS measurement. The detailed conditions for the LC / MS measurement are as follows. LC; Apparatus: Waters, UPLC Column: Waters, ACQUITY UPLC BEH C8 1.7 μm (2.1 mm I.D. × 50 mm) Detection: PDA 200-400 nm Flow rate: 0.3 mL / min Mobile phase: A = water (0.1% HCOOH) B = acetonitrile (0.1% HCOOH)

[0070]

[0071] Injection volume: 0.2 μL MS; Apparatus: Waters Synapt G2 Ionization: ESI+ Measurement range: m / z 50 to 2000 Each peak area of ​​the PDA chromatogram at 300 nm obtained by the above LC / MS measurement is determined, and the peak areas of the aromatic amine compound (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) are calculated from the peak area ratio according to the following calculation formula (1). The ratio of each peak area is calculated from the sum of all the obtained peak areas using the following calculation formula (1): Ratio of aromatic amine compound (%): [(peak area of ​​amine compound) / {(peak area of ​​amine compound)+(peak area of ​​mono-adduct)+(peak area of ​​multi-adduct)}]×100 (calculation formula (1))

[0072] <Epoxy Resin Composition> The epoxy resin composition of the first embodiment contains the epoxy resin curing agent of the first embodiment, an epoxy resin (B), and an inorganic filler (C).

[0073] <Epoxy Resin (B)> As the epoxy resin, any commonly used epoxy resin can be used without any particular limitation. For example, an epoxy resin having two or more epoxy groups per molecule is preferred. The epoxy resin may be solid or liquid at room temperature, but from the viewpoint of filling properties, it is preferable that it is liquid at room temperature. The epoxy resin may particularly be an epoxy resin that is liquid at room temperature (hereinafter also referred to as "liquid epoxy resin"), and commonly used liquid epoxy resins can be used. The liquid epoxy resin preferably has a viscosity of, for example, 0.0001 to 10 Pa·s as measured with an E-type viscometer at room temperature.

[0074] Examples of epoxy resins include diglycidyl ether epoxy resins such as bisphenol-type epoxy resins (e.g., bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A); epoxy resins obtained by epoxidizing novolac resins obtained from phenols and aldehydes, such as orthocresol novolac epoxy resins; glycidyl ester epoxy resins obtained by reacting polybasic acids (e.g., phthalic acid and dimer acid) with epichlorohydrin; glycidylamine epoxy resins obtained by reacting amine compounds (e.g., p-aminophenol, diaminodiphenylmethane, and isocyanuric acid) with epichlorohydrin; linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; 1,4-cyclohexanedimethanol diglycidyl ether; and products of epoxidation of pentaerythritol tetraallyl ether with hydrogen peroxide. These epoxy resins may be used alone or in combination of two or more.

[0075] Among these, from the viewpoint of fluidity, for example, bisphenol-type epoxy resins, glycidylamine-type epoxy resins obtained by reacting p-aminophenol with epichlorohydrin, 1,4-cyclohexanedimethanol diglycidyl ether, and products of epoxidation reaction of pentaerythritol tetraallyl ether with hydrogen peroxide are preferred. Furthermore, from the viewpoints of heat resistance, adhesion, and fluidity, for example, the above-mentioned glycidylamine-type epoxy resins are preferred. The epoxy resin is preferably one or more selected from the group consisting of bisphenol-type epoxy resins and glycidylamine-type epoxy resins. From the viewpoint of fluidity, the bisphenol-type epoxy resin is preferably one or more selected from the group consisting of bisphenol A diglycidyl ether epoxy resins (bisphenol A-type epoxy resins) and bisphenol F diglycidyl ether epoxy resins (bisphenol F-type epoxy resins). From the viewpoint of fluidity, both the bisphenol-type epoxy resins and the glycidylamine-type epoxy resins are preferably liquid at room temperature. The bisphenol-type epoxy resin and the glycidylamine-type epoxy resin may be used alone or in combination of two or more. From the viewpoints of heat resistance, adhesion, and fluidity, it is preferable to use a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin in combination. The total content of the bisphenol-type epoxy resin and the glycidylamine-type epoxy resin is not particularly limited, but from the viewpoints of heat resistance, adhesion, and fluidity, it is preferably, for example, 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more, relative to the total amount of epoxy resin. There is no particular upper limit to the total content, and it can be determined within a range that achieves desired properties and characteristics from the viewpoints of viscosity, glass transition temperature, heat resistance, etc., and may be 100% by mass.

[0076] When a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin are used in combination, the mass ratio (bisphenol-type epoxy resin:glycidylamine-type epoxy) is not particularly limited, but from the viewpoints of heat resistance, adhesion, and fluidity, it is preferably, for example, 20:80 to 95:5, more preferably 40:60 to 90:10, and even more preferably 60:40 to 80:20. Furthermore, in the first embodiment, an epoxy resin that is solid at room temperature can also be used. From the viewpoint of fluidity, the content of the epoxy resin that is solid at room temperature is, for example, preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0 to 5 mass%, relative to the total amount of epoxy resin. The epoxy equivalent of the epoxy resin is not particularly limited, but from the viewpoint of heat resistance, it is preferably 60 to 400 g / mol, more preferably 70 to 300 g / mol, and even more preferably 80 to 250 g / mol. Here, the epoxy equivalent is the mass (g / eq) of resin per epoxy group and can be measured according to the method specified in JIS K 7236. Specifically, using a Mitsubishi Chemical Analytech Corporation automatic titrator "GT-200 Model," 2 g of epoxy resin is weighed into a 200 ml beaker, 90 ml of methyl ethyl ketone is added dropwise, and the mixture is dissolved in an ultrasonic cleaner. 10 ml of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the mixture is titrated with a 0.1 mol / L perchloric acid / acetic acid solution. The purity of the epoxy resin is preferably high. In particular, the amount of hydrolyzable chlorine is preferably low because it is involved in corrosion of aluminum wiring on elements such as integrated circuits (ICs). From the viewpoint of excellent moisture resistance, for example, a level of 500 ppm or less is preferable. Here, the amount of hydrolyzable chlorine is measured by dissolving 1 g of a sample epoxy resin in 30 ml of dioxane, adding 5 ml of a 1N KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then determining the amount of hydrolyzable chlorine by potentiometric titration.The content of the epoxy resin is not particularly limited, but from the viewpoints of heat resistance, adhesiveness, and flowability, it is, for example, preferably 40 to 90 mass %, more preferably 50 to 80 mass %, and even more preferably 55 to 70 mass %, of the total amount of the epoxy resin composition excluding the (C) inorganic filler.

[0077] <Inorganic Filler (C)> The inorganic filler is not particularly limited, and examples thereof include powders such as silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, and titania, as well as beads obtained by spheronizing these powders, and glass fibers.

[0078] The inorganic filler may be an inorganic filler having a flame retardant effect, such as aluminum hydroxide, magnesium hydroxide, zinc borate, or zinc molybdate.

[0079] The inorganic filler may be used alone or in combination of two or more. Among these, from the viewpoints of availability, chemical stability, and material cost, for example, silica is preferred, and sol-gel silica and fused silica are more preferred. The particle shape of the inorganic filler is not particularly limited and may be amorphous or spherical, but from the viewpoints of fluidity and permeability into fine gaps in the epoxy resin composition, spherical silica, particularly spherical fused silica and sol-gel silica, is preferably used.

[0080] In addition, the inorganic filler may be surface-treated. Specifically, the inorganic filler may be surface-treated using a silane coupling agent. Examples of the silane coupling agent 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, isocyanurate silane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents.

[0081] The volume-average particle size of the inorganic filler is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, and even more preferably 0.5 to 3 μm. By setting the volume-average particle size of the inorganic filler to 0.1 μm or more, dispersibility in the epoxy resin is improved, the epoxy resin composition is less likely to be imparted with thixotropy, and the flow characteristics of the epoxy resin composition tend to be improved. On the other hand, by setting the volume-average particle size to 10 μm or less, sedimentation of the inorganic filler in the epoxy resin composition tends to be easily suppressed, and the permeability and flowability of the epoxy resin composition into fine gaps tend to be improved, thereby suppressing the occurrence of voids and unfilled portions. The volume-average particle size refers to the particle size at the point corresponding to 50% volume when a cumulative frequency distribution curve of particle size is calculated, assuming the total volume of the particles to be 100%. This can be measured using a particle size distribution analyzer using a laser diffraction / scattering method.

[0082] The content of the inorganic filler is not particularly limited, but is preferably 40% by mass to 70% by mass relative to the total amount of the epoxy resin composition. By setting the content of the inorganic filler to 40% by mass or more, the effect of reducing the thermal expansion coefficient and the effect of improving temperature cycle resistance tend to be easily obtained. By setting the content of the inorganic filler to 70% by mass or less, the increase in viscosity of the epoxy resin composition tends to be suppressed, and the flowability, penetration, and dispensability tend to be improved. In particular, from the viewpoint of the effect of improving temperature cycle resistance, the higher the lower limit of the content of the inorganic filler, the more preferable. In the first embodiment, even if the content of the inorganic filler is increased as described above, it is possible to maintain a low viscosity of the epoxy resin composition.

[0083] <Curing Accelerator (D)> The epoxy resin composition of the first embodiment preferably further contains a curing accelerator (D). The curing accelerator (D) is preferably at least one selected from the group consisting of compounds (D-1) represented by formula (4), formula (5), or formula (6), and imidazole-based compounds (D-2).

[0084] (Compound (D-1)) Compound (D-1) is represented by the following formula (4), (5) or (6).

[0085]

[0086]

[0087]

[0088] (In formulas (4) to (6), R １ each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. ５represents a negatively charged nitrogen atom, R ６ represents a positively charged nitrogen atom.)

[0089] In formula (4), formula (5) or formula (6), R １ is presumed to contribute to lowering the energy of the N-N bond cleavage. ２ and R ３ It is speculated that this contributes to the lowering of the energy of the cleavage reaction due to instability caused by steric hindrance. ４ It is presumed that these groups contribute to liquefying the compound and preventing a decrease in the glass transition temperature of the resulting cured product. Each group will be described in detail below.

[0090] In formulas (4), (5) and (6), R １ each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond.

[0091] R １ Among these, the organic group is not particularly limited, but examples thereof include a hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted with a hydroxyl group or a carbonyl group, and a group in which a part of the carbon atoms in a hydrocarbon group is substituted with an ester bond or an ether bond.

[0092] R １ Among these, examples of the hydrocarbon group 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, octynyl, decynyl, dodecynyl, hexadecynyl, and octadecynyl groups; aryl groups such as phenyl; and aralkyl groups including a combination of an alkyl group and a phenyl group, such as methylphenyl, ethylphenyl, and propylphenyl groups.

[0093] R １The organic group may have other substituents. The substituents are not particularly limited, but examples thereof include a halogen atom, an alkoxy group, a carbonyl group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, and an aldehyde group. １ Among these, the number of carbon atoms in the organic group is 1 to 15, preferably 1 to 12, and more preferably 1 to 7. When the number of carbon atoms in the organic group is within the above range, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved. Furthermore, when the number of carbon atoms in the organic group is within the above range, the availability of raw materials is further improved.

[0094] R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms.

[0095] R ２ and R ３ Among these, the alkyl group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl; branched alkyl groups such as isopropyl, isobutyl, t-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, and 2-dodecyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, and cyclododecyl. The alkyl group may be a linear alkyl group or an alkyl group containing a combination of a branched alkyl group and a cyclic alkyl group. Furthermore, the alkyl group may contain an unsaturated bond group.

[0096] R ２ and R ３The number of carbon atoms in the alkyl groups is, independently, 1 to 12, preferably 2 to 10, and more preferably 5 to 10. Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl groups (such as dimethylhydrazine) may be explosive and may be toxic to the human body. ２ and R ３ By making the number of carbon atoms of the alkyl group in R 2 or more, it is possible to avoid using raw materials that pose the risk of toxicity, etc. ２ and R ３ By making the number of carbon atoms in the alkyl group 5 or more, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved.

[0097] R ２ and R ３ Among them, the aryl group is not particularly limited, but examples thereof include a phenyl group and a naphthyl group.

[0098] R ２ and R ３ Among them, the aralkyl group is not particularly limited, but examples thereof include a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.

[0099] Among these, R ２ and R ３ As R, an aralkyl group is preferred, and a methylphenyl group (benzyl group) is more preferred. This tends to further improve the curing performance of the compound. ２ or R ３ The number of carbon atoms in the aryl group and aralkyl group represented by the formula (I) is not particularly limited, but is 6 to 20.

[0100] R ２ and R ３ Among these, the substituent of the alkyl group, aryl group, or aralkyl group is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a carbonyl group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, and an aldehyde group.

[0101] R ２ and R ３may be linked to form a heterocycle having 7 or less carbon atoms. The heterocycle is not particularly limited, and examples thereof include 4-membered rings such as an azetidine ring; 5-membered rings such as a pyrrolidine ring, a pyrrole ring, a morpholine ring, and a thiazine ring; 6-membered rings such as a piperidine ring; and 7-membered rings such as a hexamethyleneimine ring and an azepine ring. Among these, the heterocycle is preferably a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, or an azepine ring, with 6-membered rings and 7-membered rings being more preferred. The presence of such a group makes it easier to obtain a liquid compound and tends to further improve the curing performance of the compound.

[0102] The substituent is not particularly limited, but may be, for example, an alkyl group, an aryl group, or the above-mentioned R ２ and R ３ Furthermore, when the heterocycle has an alkyl group as a substituent, R ６ and a methyl group bonded to a carbon atom adjacent to the carbon atom.

[0103] In formulas (4), (5) and (6), R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms and optionally containing an oxygen atom. ４ Among them, the organic group is not particularly limited, but examples thereof include a hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted with a hydroxyl group, a carbonyl group, or a group containing a silicon atom, and a group in which a part of the carbon atoms in a hydrocarbon group is substituted with an ester bond, an ether bond, or a silicon atom. ４ Among these, examples of the hydrocarbon group 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, octynyl, decynyl, dodecynyl, hexadecinyl, and octadecynyl groups; aryl groups such as phenyl; and aralkyl groups including a combination of an alkyl group and a phenyl group, such as methylphenyl, ethylphenyl, and propylphenyl groups.

[0104] R ４ Among these, the hydrocarbon group may include a bisphenol skeleton such as a bisphenol A skeleton, a bisphenol AP skeleton, a bisphenol B skeleton, a bisphenol C skeleton, a bisphenol E skeleton, or a bisphenol F skeleton. The organic group containing a bisphenol skeleton is not particularly limited, but examples thereof include groups in which a polyoxyalkylene group is added to the hydroxyl group of each bisphenol skeleton.

[0105] Among these, R in formula (4) or formula (5) ４ The organic group represented by the formula (I) is preferably an alkyl group, an alkenyl group, or an aralkyl group, more preferably an alkyl group or an alkenyl group, and even more preferably a branched alkyl group or a branched alkenyl group. These preferred groups may have a substituent. By having such a group, it is easy to obtain a liquid compound having an appropriate viscosity, and the curing performance of the compound tends to be further improved. In addition, the Tg of the cured product obtained using the compound tends to be further improved.

[0106] R ４ The number of carbon atoms in the organic group is 1 to 50, preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8. ４ When the number of carbon atoms in the organic group is within the above range, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved. In addition, the Tg of the cured product obtained using this compound is further improved, and further, ４ When the number of carbon atoms of the organic group in the hydroxyl group is within the above range, the availability of raw materials is further improved.

[0107] Among the above, R in formula (4) or formula (5) ４is preferably a linear or branched alkyl group having 3 to 12 carbon atoms, and a linear or branched alkenyl group having 3 to 6 carbon atoms. By containing such a group, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved. From the viewpoint of curing temperature control or viscosity control, it is preferable that compound (D-1) contains a plurality of compounds represented by formula (4), formula (5), or formula (6). It is also possible to contain a plurality of compounds having different structures represented by the same formula.

[0108] In particular, from the viewpoint of viscosity control, compound (D-1) preferably contains compounds represented by formula (4) and formula (6). When a plurality of compounds represented by formula (4), (5), or (6) are contained, the content ratio of the compound represented by formula (4) is preferably 0.1% by mass to 99.5% by mass relative to the total amount of the compounds represented by formula (4), (5), or (6). This makes it possible to easily control the viscosity. A composition containing a plurality of compounds represented by formula (4), (5), or (6) can be obtained by mixing the plurality of compounds, or by simultaneously producing the plurality of compounds in the compound production method described below.

[0109] The compound represented by formula (4), formula (5), or formula (6) can be produced, for example, by reacting an ester compound, a hydrazine compound, and a glycidyl ether compound, although this is not limited thereto.

[0110] The ester compound is not particularly limited, but examples thereof include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds.

[0111] Specific examples of monocarboxylic acid ester compounds include methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonate, methyl benzoylformate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl, etc. Alternatively, ethyl esters, propyl esters, etc. may be used.

[0112] Specific examples of dicarboxylic acid ester compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate. Alternatively, cyclic esters may be used. Specific examples of cyclic esters include α-acetolactone, β-propionolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, and ε-caprolactone. Alternatively, diethyl esters, dipropyl esters, and the like may be used.

[0113] Among these, from the viewpoint of curability and liquefaction, the ester compound is preferably 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 crotonate, methyl isocrotonate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelaate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, γ-butyrolactone, δ-valerolactone, or γ-valerolactone.

[0114] The hydrazine compound is not particularly limited, but examples thereof include dimethylhydrazine, diethylhydrazine, methylethylhydrazine, methylpropylhydrazine, methylbutylhydrazine, methylpentylhydrazine, methylhexylhydrazine, ethylpropylhydrazine, ethylbutylhydrazine, ethylpentylhydrazine, ethylhexylhydrazine, dipropylhydrazine, dibutylhydrazine, dipentylhydrazine, dihexylhydrazine, methylphenylhydrazine, ethylphenylhydrazine, methyltolylhydrazine, ethyltolylhydrazine, diphenylhydrazine, benzylphenylhydrazine, dibenzylhydrazine, dinitrophenylhydrazine, 1-aminopiperidine, N-aminohomopiperidine, 1-amino-2,6-dimethylpiperidine, 1-aminopyrrolidine, 1-amino-2-methylpyrrolidine, 1-amino-2-phenylpyrrolidine, and 1-aminomorpholine. Among these, from the viewpoints of curability and liquefaction, dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred as the hydrazine compound. Furthermore, among these, from the viewpoints of availability and safety, dibenzylhydrazine and 1-aminopiperidine are more preferred. The hydrazine compounds may be used alone or in combination of two or more.

[0115] The glycidyl ether compound is not particularly limited, but for example, a monofunctional monoglycidyl ether compound, a bifunctional or higher functional polyglycidyl ether compound, or the like can be used.

[0116] Specific examples of the monoglycidyl ether compound include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, orthophenylphenol glycidyl ether, benzyl glycidyl ether, biphenylyl glycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, and 3-[diethoxy(methyl)silyl]propyl glycidyl ether.

[0117] Specific examples of polyglycidyl ether compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, and glycerin polyglycidyl ether. alicyclic polyglycidyl ether compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ethylene oxide-added bisphenol A diglycidyl ether, propylene oxide-added bisphenol A diglycidyl ether, and hydrogenated condensates thereof; and aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether.

[0118] Among these, from the viewpoint of curability and liquefaction, preferred glycidyl ether compounds include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, ethylene oxide adduct bisphenol A diglycidyl ether, propylene oxide adduct bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, and 1-phenoxy-1,4-(oxiranylmethoxy)-3,6,9,12-tetraoxatetradecane.

[0119] Furthermore, from the viewpoint of adhesiveness, epoxy resins having an ether structure are preferred. Specific examples include polyethylene glycol diglycidyl ether and 1-phenoxy-1,4-(oxiranylmethoxy)-3,6,9,12-tetraoxatetradecane. The glycidyl ether compounds may be used alone or in combination of two or more.

[0120] The amounts of the ester compound, hydrazine compound, and glycidyl ether compound added to the reaction system can be set based on the molar ratio of the functional groups. The amount of the ester group of the ester compound is preferably 0.8 mol to 3.0 mol, more preferably 0.9 mol to 2.8 mol, and even more preferably 0.95 mol to 2.5 mol, relative to 1 mol of the primary amine of the hydrazine compound. The amount of the glycidyl group of the glycidyl ether compound is preferably 0.8 mol to 2.0 mol, more preferably 0.9 mol to 1.5 mol, and even more preferably 0.95 mol to 1.4 mol, relative to 1 mol of the primary amine of the hydrazine compound.

[0121] By controlling the amount of glycidyl groups in the glycidyl ether compound added relative to 1 mole of the primary amine in the hydrazine compound, compositions containing the compounds represented by formula (5) and formula (4) can be simultaneously produced. Specifically, the amount of glycidyl groups in the glycidyl ether compound is preferably 0.1 mol to 3.0 mol, more preferably 0.3 mol to 2.0 mol, and even more preferably 0.5 mol to 1.0 mol, relative to 1 mole of the primary amine in the hydrazine compound. In the above-mentioned methods for producing the compounds and compositions, a solvent may be used from the viewpoint of uniformly progressing the reaction.

[0122] The solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.

[0123] The reaction temperature is preferably 10 to 100° C., more preferably 40 to 90° C. When the reaction temperature is 10° C. or higher, the reaction proceeds quickly, and the purity of the resulting compound tends to be improved. Furthermore, when the reaction temperature is 90° C. or lower, the polymerization reaction between glycidyl ether compounds can be efficiently suppressed, and the purity of the compound tends to be improved.

[0124] The reaction time is preferably 1 hour or more and 168 hours or less, more preferably 1 hour or more and 96 hours or more, and even more preferably 1 hour or more and 48 hours or less. After completion of the reaction, the obtained reaction product can be purified by known purification methods such as washing, extraction, recrystallization, column chromatography, etc. For example, the reaction solution dissolved in an organic solvent is washed with water, and then the organic layer is heated under normal pressure or reduced pressure to remove unreacted raw materials and the organic solvent from the reaction solution, and the target compound can be recovered. The target compound can also be recovered by purification using column chromatography. The solvent used for the above-mentioned washing is not particularly limited as long as it can dissolve the residual raw materials, but 1-hexane, 1-pentane, and cyclohexane are preferred from the viewpoints of yield, purity, and ease of removal.

[0125] The organic solvent used in the extraction is not particularly limited as long as it can dissolve the target compound. From the viewpoints of yield, purity, and ease of removal, however, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred.

[0126] The packing material used in column chromatography may be a known one such as alumina, silica gel, etc. The developing solvent may be a known one such as ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, etc., which may be used alone or in combination.

[0127] In the epoxy resin curing agent of the first embodiment, it is preferable that n in formula (5) and formula (6) of compound (D-1) is 2 or 3. This improves the crosslink density during curing, making it possible to prepare a tough cured product, and improving adhesion and reliability.

[0128] (Imidazole Compound (D-2)) The imidazole compound (D-2) can be used without any particular limitation. Examples of the imidazole compound (D-2) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, imidazolyl succinic acid, 2-methylimidazole succinic acid, 2-ethylimidazole succinic acid, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole.

[0129] From the viewpoint of permeability, the epoxy resin composition of the first embodiment has a viscosity at 25°C of preferably 50 Pa s or less, more preferably 40 Pa s or less, and even more preferably 20 Pa s or less. From the viewpoint of suppressing bleeding, the epoxy resin composition of the first embodiment has a viscosity at 25°C of preferably 0.1 Pa s or more, more preferably 1 Pa s or more, and even more preferably 2 Pa s or more.

[0130] The viscosity (Pa s) of the epoxy resin composition at 25°C is obtained by dropping the epoxy resin composition into a measuring cup and measuring the viscosity with an E-type viscometer (for example, "TV-20" manufactured by Toki Sangyo Co., Ltd.) 5 minutes after the sample temperature reaches 25°C (cone No. 5, 3°, R=12 mm).

[0131] The epoxy resin composition of the first embodiment preferably has a viscosity (η2) of 0.01 Pa s to 1.50 Pa s, more preferably 0.01 Pa s to 1.0 Pa s, and even more preferably 0.01 Pa s to 0.5 Pa s after being left at 110°C for 60 minutes. The viscosity after being left at 110°C for 60 minutes is measured using a rheometer (for example, a HAAKE MARS manufactured by Thermo Scientific).

[0132] The epoxy resin composition of the first embodiment preferably exhibits a viscosity increase rate of 1.0 to 40.0 times, more preferably 1.0 to 30 times, and even more preferably 1.0 to 20 times after being left at 110°C for 60 minutes. The viscosity increase rate after being left at 110°C for 60 minutes is measured using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) with an aluminum cone plate R=20 mm and a shear rate of 20 ( / sec) after the epoxy resin composition is dropped onto a measurement plate and the viscosity increase rate is measured 5 minutes and 60 minutes after the sample temperature reaches 110°C. The viscosity increase rate is calculated by η2 / η1, where "η1" is the viscosity after 5 minutes and "η2" is the viscosity after 60 minutes.

[0133] The epoxy resin composition of the first embodiment preferably has a reaction rate of 70% or more and 100% or less, more preferably 80% or more and 100% or less, and even more preferably 90% or more and 100% or less, when cured at 165°C.

[0134] The reaction rate when an epoxy resin composition is cured at 165°C is determined by using an EXSTER6000 (Hitachi High-Tech Science Corporation) to raise the temperature from 25°C to 300°C at a rate of 5°C / min, and calculating the total amount of heat generated in the temperature range from 100°C to 250°C. Furthermore, similar measurements may be taken after placing the composition in a small high-temperature chamber (manufactured by Espec Corporation) at 180°C for 2 hours, and the change in heat generated in the same temperature range may be calculated as a percentage. Furthermore, similar measurements may be taken after placing the composition in a small high-temperature chamber (manufactured by Espec Corporation) at 165°C for 2 hours, and the change in heat generated in the same temperature range may be calculated as a percentage. The calculation formula is as follows: Initial heat generation amount A: DSC peak heat generation amount of the composition; Post-curing heat generation amount B: DSC peak heat generation amount of the composition after heating; Reaction rate (%) = 100 × (Initial heat generation amount A - Post-curing heat generation amount B) ÷ Initial heat generation amount A

[0135] The epoxy resin composition and cured product of the first embodiment are useful as adhesives, encapsulants, filler materials, insulating materials, conductive materials, anisotropic conductive materials, sealing materials, prepregs, etc. As adhesives, they are useful as liquid adhesives, film adhesives, die bonding materials, etc. As encapsulants, they are useful as solid encapsulants, liquid encapsulants, film encapsulants, etc., and as liquid encapsulants, they are useful as underfill materials, potting materials, dam materials, etc. As insulating materials, they are useful as insulating adhesive films, insulating adhesive pastes, solder resists, etc.; as conductive materials, they are useful as conductive films, conductive pastes, etc.; and as anisotropic conductive materials, they are useful as anisotropic conductive films, anisotropic conductive pastes, etc.

[0136] <<Adhesive>> The epoxy resin composition of the first embodiment can be suitably used as an adhesive. The adhesive of the first embodiment contains the epoxy resin composition of the first embodiment.

[0137] <<Cured Product>> The cured product of the first embodiment is a cured product of the epoxy resin composition of the first embodiment. The cured product of the first embodiment can be suitably used as a sealant, and the sealant is preferably a semiconductor sealant. The sealant of the first embodiment includes the cured product of the first embodiment.

[0138] Furthermore, the cured product of the first embodiment can be suitably used as a semiconductor package. The semiconductor package of the first embodiment includes the cured product of the first embodiment. A method for producing a semiconductor package of the first embodiment includes a step of producing a semiconductor package using the epoxy resin composition of the first embodiment. The step of producing a semiconductor package using the epoxy resin composition of the first embodiment may include a step of preparing the epoxy resin composition of the first embodiment. The epoxy resin composition of the first embodiment may be obtained, for example, by stirring and mixing the components contained in the epoxy resin composition of the first embodiment in a planetary centrifugal mixer (for example, "ARE-310" manufactured by Thinky Corporation), followed by kneading with a three-roll mill.

[0139] The process for producing a semiconductor package using the epoxy resin composition of the first embodiment may be a process for producing a semiconductor package by appropriately molding a prepared epoxy resin composition and heating it at a predetermined temperature for a predetermined time to cure it.

[0140] Second Embodiment Epoxy Resin Curing Agent An epoxy resin curing agent of a second embodiment comprises an aromatic amine compound (A-1) and an aromatic amine adduct (A-2) that is a reaction product of the aromatic amine compound and a reactive compound having a functional group capable of reacting with the aromatic amine compound, and has a glass transition temperature (Tg) of 20°C or lower as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5°C / min.

[0141] The epoxy resin curing agent of the second embodiment contains the above-described components, and thus after being mixed with an epoxy resin, can have excellent permeability and can achieve both curability and storage stability.

[0142] <Glass Transition Temperature (Tg)> The epoxy resin curing agent of the second embodiment has a glass transition temperature (Tg) of 20°C or lower, as detected by differential scanning calorimetry (DSC analysis) at a temperature rise rate of 5°C / min. A Tg of 20°C or lower can suppress viscosity changes in high-temperature environments during penetration and during storage, resulting in excellent penetration properties. From the above viewpoints, the Tg is more preferably 5°C or lower, even more preferably 0°C or lower, and particularly preferably -20°C or lower. On the other hand, from the viewpoint of excellent heat resistance, the Tg is preferably -40°C or higher, more preferably -30°C or higher, and even more preferably -20°C or higher.

[0143] The glass transition temperature (Tg) of an epoxy resin curing agent is measured by the following method. Using a differential scanning calorimeter (for example, a differential scanning calorimeter system "DSC Q2000" manufactured by TA Instruments-Waters), a 10 mg sample is heated from -50°C to 200°C at a heating rate of 5°C / min under a nitrogen gas flow (40 mL / min). The Tg of the epoxy resin curing agent is the peak top temperature of the DSC differential curve (JIS K6240:2011).

[0144] In order to achieve a glass transition temperature (Tg) of 10°C (preferably 5°C) or less, it is preferable to use a compound that does not have a melting point in the range of -20°C to 60°C as the aromatic amine compound (A-1). For example, Ethacure 100+, represented by formula (12), is an aromatic amine compound that is liquid at room temperature. The amine adduct obtained by reacting it with a reactive compound is also liquid, and its Tg is 10°C or less. It is also preferable to use a skeleton having a flexible substituent in the molecular skeleton as the aromatic amine compound (A-1), and a compound having an alkyl chain as the reactive compound. For example, 4-aminophenyl-4-aminobenzoate has a flexible ester bond in its skeleton, and by reacting it with 2-ethylhexyl glycidyl ether, a reactive compound having an alkyl group, its Tg is 10°C or less. Furthermore, a Tg of 20°C or less can also be achieved by reacting more than 1 mol of a reactive compound with 1 mol of aromatic amine compound (A-1).

[0145] <Aromatic Amine Compound (A-1)> The epoxy resin curing agent of the second embodiment contains an aromatic amine compound (A-1). The aromatic amine compound (A-1) is preferably an aromatic amine compound represented by the following formula (11) or (12):

[0146]

[0147] In formula (11), R α and R β each independently represents 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.

[0148] R α and R β In the formula (I), the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. a and b are each independently an integer of 0 to 2, and more preferably 0 or 1. In the formula (I), the divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0149] Examples of aromatic amines represented by formula (11) include 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-4-aminobenzoate, 2-fluoro-4-aminophenyl-4-aminobenzoate, 3-fluoro-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-3-methyl-4-aminobenzoate, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether ... , 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 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-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-biphenyl bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, 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, 4,4'-diamino-3,3'-5,Among these, from the viewpoint of achieving both curability and stability when combined with an epoxy resin, the aromatic amine represented by formula (11) is preferably selected from the group consisting of -CO-, -C(=O)O-, -SO, ２ Aromatic amines having a - or -C(=O)NH- bond are preferred, and among these, aromatic amines having a -C(=O)O- bond are more preferred.

[0150]

[0151] In formula (12), R γ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and c is an integer of 1 to 4. γ In the formula (I), the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. c is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0152] Examples of aromatic amines represented by formula (12) include diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, etc., and it is preferable to use one or more selected from these. Among these, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene) is preferred as the aromatic amine represented by formula (12) from the viewpoint of achieving both curability and stability when formed into a composition with an epoxy resin.

[0153] <Aromatic Amine Adduct (A-2)> The aromatic amine adduct (A-2) is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).

[0154] (Reactive Compound) The reactive compound has a functional group capable of reacting with the aromatic amine compound (A-1). Examples of the functional group include a carboxyl group, a sulfo group, an isocyanato group, a carbonyl group, and an epoxy group.

[0155] The reactive compound has a functional group capable of reacting with the aromatic amine compound (A-1). Examples of the functional group include a -C(=O)OC(=O)- group, a carboxyl group, a sulfo group, an isocyanato group, a carbonyl group, an epoxy group, a fluoro group, a chloro group, a bromo group, and an iodo group. The reactive compound is preferably at least one compound selected from the group consisting of an acid anhydride, an acid dianhydride, a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound, an epoxy compound, and an alkyl halide.

[0156] Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

[0157] Examples of sulfonic acid compounds include ethanesulfonic acid and p-toluenesulfonic acid.

[0158] Examples of isocyanate compounds include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates. Examples of aliphatic diisocyanates include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of alicyclic diisocyanates include isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, and 1,3-bis(2-isocyanatopropyl-2-yl)-cyclohexane. Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of aliphatic triisocyanates include 1,3,6-triisocyanatomethylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl. Examples of polyisocyanates include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above diisocyanate compounds. Examples of polyisocyanates derived from the above diisocyanates include isocyanurate-type polyisocyanates, biuret-type polyisocyanates, urethane-type polyisocyanates, allophanate-type polyisocyanates, and carbodiimide-type polyisocyanates.

[0159] Examples of the urea compound include urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.

[0160] The epoxy compound may be a monoepoxy compound, a polyepoxy compound, or a mixture thereof. Examples of the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.Examples of polyfunctional 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 dihydric 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; and epoxy compounds obtained by glycidylating tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. compounds; novolac-type epoxy compounds obtained by glycidylating novolacs such as phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and brominated bisphenol A novolac; aliphatic ether-type epoxy compounds obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol; ether ester-type epoxy compounds obtained by glycidylating hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid; ester-type epoxy compounds obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl-type epoxy compounds such as epoxy compounds obtained by glycidylating amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and epoxy compounds obtained by glycidylating amine-type epoxy compounds such as triglycidyl isocyanurate; and alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate.

[0161] Among the above, from the viewpoint of excellent curability and storage stability, the reactive compound is preferably an epoxy compound, and more preferably an epoxy compound having one glycidyl group in the molecule.

[0162] In order to achieve both high curability and storage stability, the total chlorine content of the epoxy compound is preferably 400 ppm or less. It is more preferably 300 ppm or less, even more preferably 200 ppm or less, particularly preferably 180 ppm or less, even more preferably 171 ppm or less, even more preferably 100 ppm or less, particularly preferably 80 ppm or less, and even more preferably 50 ppm or less. In the second embodiment, the total chlorine content refers to the total amount of organic chlorine and inorganic chlorine contained in the compound, and is a value based on the mass of the compound. Of the total chlorine, the chlorine contained in 1,2-chlorohydrin groups is generally referred to as hydrolyzable chlorine. The amount of hydrolyzable chlorine in the epoxy compound used in the second embodiment is preferably 50 ppm or less, more preferably 0.01 to 20 ppm, and even more preferably 0.05 to 10 ppm. A hydrolyzable chlorine content of 50 ppm or less is advantageous for achieving both high curability and storage stability, and is preferred because it exhibits excellent electrical properties. In the second embodiment, when it is desired to reduce the total chlorine content of an epoxy compound, examples include a method in which a dechlorination reaction is carried out using a base catalyst in an aprotic solvent, and then the epoxy compound is purified by washing with water, and a method in which a dechlorination reaction is carried out using a metal amide compound such as a bis(trialkylsilyl)amide metal salt as a catalyst, and then the epoxy compound is purified by washing with water.

[0163] The aromatic amine adduct (A-2) is a reaction product of an aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1). The aromatic amine adduct (A-2) used in the second embodiment can be obtained, for example, by reacting 1 to 5 moles of the aromatic amine compound (A-1) with 1 to 5 moles of a reactive compound (e.g., an epoxy compound) in the presence of a solvent, for example, at a temperature of 50 to 250°C for 0.1 to 10 hours, and then removing the unreacted aromatic amine compound (A-1) and the solvent, as necessary. The solvent used here is not particularly limited, but examples thereof include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, etc.; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, etc.; water, etc., and these solvents may be used in combination.

[0164] The epoxy resin curing agent of the second embodiment preferably has at least one melting point (Tm) of 60°C or less as detected by differential scanning calorimetry (DSC analysis) at a temperature rise rate of 5°C / min. A Tm of 60°C or less can suppress viscosity changes in high-temperature environments during penetration and during storage, resulting in excellent penetration properties. From the above viewpoints, Tm is more preferably 60°C or less, even more preferably 50°C or less, and particularly preferably 40°C or less. On the other hand, from the viewpoint of excellent heat resistance, Tm is preferably -40°C or more, more preferably -30°C or more, and even more preferably -20°C or more.

[0165] Alternatively, the epoxy resin curing agent of the second embodiment preferably has a melting point (Tm) that is not detected in the range of -20°C to 60°C in differential scanning calorimetry (DSC analysis) measured at a temperature range of -50°C to 200°C and a heating rate of 5°C / min. When the compound having the structure represented by formula (11) or (12) has a substituent on the side chain, intermolecular interactions are inhibited, and the compound is amorphous. In other words, when a melting point (Tm) is not detected in the range of -20°C to 60°C, the viscosity at the temperature during penetration and the penetration properties are excellent.

[0166] In order to achieve a glass transition temperature (Tm) of 60°C or less, it is preferable to use a compound that does not have a melting point in the range of -20°C to 60°C as the aromatic amine compound (A-1). For example, Ethacure 100+, represented by formula (12), is an amorphous aromatic amine compound that is liquid at room temperature. The amine adduct obtained by reacting it with a reactive compound is also liquid and amorphous, and therefore does not observe a Tm in the range of -20°C to 60°C. It is also preferable to use a skeleton having a flexible substituent in the molecular skeleton as the aromatic amine compound (A-1), and a compound having an alkyl chain as the reactive compound. For example, 4-aminophenyl-4-aminobenzoate has a flexible ester bond in its skeleton, and by reacting it with 2-ethylhexyl glycidyl ether, a reactive compound having an alkyl group, the Tm becomes 60°C or less. Furthermore, the Tm can also be reduced to 60°C or less by reacting 1 mol of aromatic amine compound (A-1) with 1 mol or more of 2-ethylhexyl glycidyl ether as a reactive compound.

[0167] The melting point (Tm) of an epoxy resin curing agent is measured by the following method. Using a differential scanning calorimeter (for example, a differential scanning calorimeter system "DSC Q2000" manufactured by TA Instruments-Waters), a 10 mg sample is heated from -50°C to 200°C at a heating rate of 5°C / min under a nitrogen gas flow (40 mL / min). The Tm of an epoxy resin curing agent is the apex temperature of the endothermic peak in the DSC curve (JIS K7121:1987).

[0168] In the epoxy resin curing agent of the second embodiment, the aromatic amine adduct (A-2) may include an aromatic amine adduct (A-2-1) in which one molecule of a reactive compound is added to one molecule of an aromatic amine compound (A-1), and an aromatic amine adduct (A-2-2X) in which two or more molecules of a reactive compound are added to one molecule of an aromatic amine compound (A-1).

[0169] In the epoxy resin curing agent of the second embodiment, the aromatic amine adduct (A-2) preferably includes an aromatic amine adduct (A-2-1) in which one molecule of a reactive compound is added to one molecule of the aromatic amine compound (A-1). Furthermore, the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1), as determined by liquid chromatography analysis (UV detector), is preferably 0.10 to 0.45. Having an (A-1 / A-2-1) ratio of 0.10 or greater provides superior curability, thereby achieving both curability and storage stability. From the above perspectives, (A-1 / A-2-1) is more preferably 0.1 or greater, even more preferably 0.12 or greater, and particularly preferably 0.15 or greater. On the other hand, having an (A-1 / A-2-1) ratio of 0.45 or less provides superior penetration. From the above viewpoints, (A-1 / A-2-1) is more preferably 0.45 or less, even more preferably 0.42 or less, and particularly preferably 0.40 or less. Therefore, by making (A-1 / A-2-1) 0.10 to 0.45, both curability and excellent permeability can be achieved more satisfactorily.

[0170] It is also preferable that the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1), as determined by liquid chromatography analysis (UV detector), is 0.50 to 2.00. When (A-1 / A-2-1) is 0.50 or more, the heat resistance of the cured product with the epoxy resin is excellent. From the above viewpoint, (A-1 / A-2-1) is more preferably 0.5 or more, even more preferably 0.75 or more, and particularly preferably 1.2 or more. On the other hand, when (A-1 / A-2-1) is 2.0 or less, the permeability and storage stability are excellent. From the above viewpoint, (A-1 / A-2-1) is more preferably 2.0 or less, even more preferably 1.9 or less, and particularly preferably 1.8 or less. Therefore, by making (A-1 / A-2-1) 0.50 to 2.00, the heat resistance is excellent when cured with the epoxy resin, and both the permeability and storage stability can be more favorably achieved.

[0171] [Analysis of Components in Epoxy Resin Curing Agent] The method for analyzing each component in the epoxy resin curing agent is as follows. After adjusting the concentration of the amine adduct synthesized in the Synthesis Example to 10% by mass with THF, a 1 mg / mL acetonitrile solution was prepared and subjected to LC / MS measurement. The detailed conditions for the LC / MS measurement are as follows. LC; Apparatus: Waters, UPLC Column: Waters, ACQUITY UPLC BEH C8 1.7 μm (2.1 mm I.D. × 50 mm) Detection: PDA 200-400 nm Flow rate: 0.3 mL / min Mobile phase: A = water (0.1% HCOOH) B = acetonitrile (0.1% HCOOH)

[0172]

[0173] Injection volume: 0.2 μL MS; Apparatus: Waters Synapt G2 Ionization: ESI+ Measurement range: m / z 50 to 2000 Each peak area of ​​the PDA chromatogram at 300 nm obtained by the above LC / MS measurement is determined, and the peak areas of the aromatic amine compound (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) are calculated from the peak area ratio according to the following calculation formula (1). The ratio of each peak area is calculated from the sum of all the obtained peak areas using the following calculation formula (1): Ratio of aromatic amine compound (%): [(peak area of ​​amine compound) / {(peak area of ​​amine compound)+(peak area of ​​mono-adduct)+(peak area of ​​multi-adduct)}]×100 (calculation formula (1))

[0174] <Epoxy Resin Composition> The epoxy resin composition of the second embodiment contains the epoxy resin curing agent of the second embodiment, an epoxy resin (B), and an inorganic filler (C).

[0175] <Epoxy Resin (B)> Details of specific examples, preferred specific examples, preferred aspects such as the content of the epoxy resin (B) in the second embodiment are the same as the details of specific examples, preferred specific examples, preferred aspects such as the content of the epoxy resin (B) in the first embodiment.

[0176] <Inorganic Filler (C)> Details of specific examples, preferred specific examples, preferred aspects such as the content of the inorganic filler (C) in the second embodiment are the same as the details of specific examples, preferred specific examples, preferred aspects such as the content of the inorganic filler (C) in the first embodiment.

[0177] <Curing Accelerator (D)> Details of preferred aspects such as specific examples, preferred specific examples, and content of the curing accelerator (D) in the second embodiment are the same as the details of preferred aspects such as specific examples, preferred specific examples, and content of the curing accelerator (D) in the first embodiment.

[0178] From the viewpoint of permeability, the epoxy resin composition of the second embodiment has a viscosity at 25°C of preferably 50 Pa·s or less, more preferably 40 Pa·s or less, and even more preferably 20 Pa·s or less.

[0179] From the viewpoint of suppressing bleeding, the epoxy resin composition of the second embodiment preferably has a viscosity at 25°C of 0.1 Pa·s or more, more preferably 1 Pa·s or more, and even more preferably 2 Pa·s or more.

[0180] The viscosity (Pa s) of the epoxy resin composition at 25°C is obtained by dropping the epoxy resin composition into a measuring cup and measuring the viscosity with an E-type viscometer (for example, "TV-20" manufactured by Toki Sangyo Co., Ltd.) 5 minutes after the sample temperature reaches 25°C (cone No. 5, 3°, R=12 mm).

[0181] The epoxy resin composition of the second embodiment preferably has a viscosity of 0.01 Pa s to 1.50 Pa s, more preferably 0.01 Pa s to 1.3 Pa s, and even more preferably 0.01 Pa s to 1.0 Pa s after being left at 110°C for 60 minutes. The viscosity after being left at 110°C for 60 minutes is measured using a rheometer (for example, a HAAKE MARS manufactured by Thermo Scientific).

[0182] The epoxy resin composition of the second embodiment preferably exhibits a viscosity increase rate of 1.0 to 40.0 times, more preferably 1 to 30 times, and even more preferably 1 to 20 times after being left at 110°C for 60 minutes. The viscosity increase rate after being left at 110°C for 60 minutes is measured using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) by dropping the epoxy resin composition onto a measurement plate and measuring the viscosity at 5 minutes and 60 minutes after the sample temperature reaches 110°C (aluminum cone plate, R = 20 mm, shear rate 20 ( / sec)). The viscosity after 5 minutes is defined as "η1" and the viscosity after 60 minutes is defined as "η2", and the viscosity increase rate is calculated by η2 / η1.

[0183] The epoxy resin composition of the second embodiment preferably has a reaction rate of 70% or more and 100% or less, more preferably 80% or more and 100% or less, and even more preferably 90% or more and 100% or less, when cured at 165°C.

[0184] The reaction rate when an epoxy resin composition is cured at 165°C or 180°C is determined, for example, by using an EXSTER 6000 (Hitachi High-Tech Science Corporation) to raise the temperature from 25°C to 300°C at a rate of 5°C / min, and calculating the total amount of heat generated in the temperature range from 100°C to 250°C. Furthermore, similar measurements may be taken after placing the composition in a small high-temperature chamber (manufactured by Espec Corporation) at 180°C for 2 hours, and the change in heat generated in the same temperature range may be calculated as a percentage. Furthermore, similar measurements may be taken after placing the composition in a small high-temperature chamber (manufactured by Espec Corporation) at 165°C for 2 hours, and the change in heat generated in the same temperature range may be calculated as a percentage. The calculation formula is as follows: Initial heat generation amount A: DSC peak heat generation amount of the composition; Post-curing heat generation amount B: DSC peak heat generation amount of the composition after heating; Reaction rate (%) = 100 × (Initial heat generation amount A - Post-curing heat generation amount B) ÷ Initial heat generation amount A

[0185] The epoxy resin composition and cured product of the second embodiment are useful as adhesives, encapsulants, filler materials, insulating materials, conductive materials, anisotropic conductive materials, sealing materials, prepregs, etc. As adhesives, they are useful as liquid adhesives, film adhesives, die bonding materials, etc. As encapsulants, they are useful as solid encapsulants, liquid encapsulants, film encapsulants, etc., and as liquid encapsulants, they are useful as underfill materials, potting materials, dam materials, etc. As insulating materials, they are useful as insulating adhesive films, insulating adhesive pastes, solder resists, etc.; as conductive materials, they are useful as conductive films, conductive pastes, etc.; and as anisotropic conductive materials, they are useful as anisotropic conductive films, anisotropic conductive pastes, etc.

[0186] <<Adhesive>> The epoxy resin composition of the second embodiment can be suitably used as an adhesive. The adhesive of the second embodiment contains the epoxy resin composition of the second embodiment.

[0187] <<Cured Product>> The cured product of the second embodiment is a cured product of the epoxy resin composition of the second embodiment. Details such as specific aspects and preferred aspects of the cured product of the second embodiment are the same as the details such as specific aspects and preferred aspects of the cured product of the first embodiment.

[0188] The first embodiment will be described below with specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. In other words, a person skilled in the art can practice the present invention by making various modifications to the examples shown below. In the following, unless otherwise specified, "parts" are based on mass.

[0189] [Analysis of Components in Epoxy Resin Curing Agent] Analysis was carried out by the method described in the above section [Analysis of Components in Epoxy Resin Curing Agent].

[0190] [Method for measuring glass transition temperature (Tg) and melting point (Tm) of epoxy resin curing agent] The glass transition temperature (Tg) and melting point (Tm) of the epoxy resin curing agent were measured using a differential scanning calorimeter (differential scanning calorimetry system, "DSC Q2000", manufactured by TA Instruments-Waters Corporation) under a nitrogen gas flow (40 mL / min) by heating a 10 mg sample from -50°C to 200°C at a heating rate of 5°C / min. The Tm of the amine adduct was taken as the apex temperature of the endothermic peak in the DSC curve (JIS K7121-1987), and the Tg was taken as the peak top temperature in the DSC differential curve (JIS K6240). The obtained Tg and Tm were evaluated according to the following evaluation criteria. [Evaluation criteria for Tg] A: Tg was -20°C or lower. B: Tg was higher than -20°C and 5°C or lower. C: Tg was more than 5°C and not more than 10°C. D: Tg was more than 10°C. [Evaluation criteria for Tm] A: No clear peak top temperature was observed. B: Tm was not less than -20°C and less than 20°C. C: Tm was not less than 20°C and not more than 60°C. D: Tm was more than 60°C.

[0191] [Method for measuring viscosity of epoxy resin composition at 25°C] The viscosity (Pa s) of the epoxy resin composition at 25°C was measured using an E-type viscometer (TV-20, manufactured by Toki Sangyo Co., Ltd.) 5 minutes after the resin composition (0.3 mL) was dropped into a measuring cup and the sample temperature reached 25°C (cone No. 5, 3°, R=12 mm). The obtained viscosity was evaluated according to the following evaluation criteria. [Evaluation criteria] A: The viscosity at 25°C was less than 10 Pa s. B: The viscosity at 25°C was 10 Pa s or more and less than 50 Pa s. C: The viscosity at 25°C was 50 Pa s or more and less than 100 Pa s. D: The viscosity at 25°C was 100 Pa s or more.

[0192] [Method for measuring viscosity of epoxy resin composition at 110°C] The viscosity (Pa s) of the epoxy resin composition at 110°C was measured using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) by dropping 0.2 mL of the resin composition onto a measurement plate and measuring the viscosity 5 minutes after the sample temperature reached 110°C (aluminum cone plate R=20 mm, shear rate 20 ( / sec)). The obtained viscosity was evaluated according to the following evaluation criteria. [Evaluation criteria] A: The viscosity at 110°C was less than 0.10 Pa s. B: The viscosity at 110°C was 0.10 Pa s or more and less than 0.20 Pa s. C: The viscosity at 110°C was 0.20 Pa s or more and less than 0.50 Pa s. D: The viscosity at 110°C was 0.50 or more.

[0193] [Method for Evaluating Viscosity Stability at 110°C (High Temperature)] The viscosity stability of the epoxy resin composition at 110°C was evaluated by dropping 0.2 mL of the resin composition onto a measurement plate. Five minutes and 60 minutes after the sample temperature reached 110°C, the viscosity was measured using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) at a constant measurement temperature (110°C) in oscillation mode (f = 1 Hz) (aluminum parallel plate R = 20 mm, 20 ( / sec)). The viscosity after 5 minutes was designated "η1" and the viscosity after 60 minutes was designated "η2." The viscosity increase ratio was calculated as η2 / η1. The obtained viscosity increase ratios were evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The viscosity increase ratio was less than 3.0 times. B: The viscosity increase ratio was 3.0 times or more but less than 10.0 times. C: The viscosity increase ratio was 10.0 times or more but less than 40.0 times. D: The viscosity increase rate was 40.0 times or more.

[0194] [Evaluation of Flow Properties] A test specimen was prepared by fixing a glass plate instead of a semiconductor element on a glass substrate (26 mm wide x 75 mm long) with a gap of 25 μm. Next, this test specimen was placed on a hot plate set at 110° C., and an epoxy resin composition was applied to one end of the glass plate. The time (seconds) required for the resin to pass through the gap and reach a point 20 mm away was measured. The obtained time was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The arrival time was less than 80 seconds. B: The arrival time was 80 seconds or more but less than 120 seconds. C: The arrival time was 120 seconds or more but less than 200 seconds. D: The arrival time was 200 seconds or more.

[0195] [Method for Measuring Tg of Cured Product] Epoxy resin compositions were cured at 165°C (180°C when no amine imide was included) for 2 hours to prepare test specimens (2 mm thick x 20 mm long x 10 mm wide). The test specimens were measured using a thermomechanical analyzer (RSA-G2, manufactured by TA Instruments Japan, Inc.) in Force Tracking mode under conditions of an initial load of 0.5 N, a measurement temperature of 0°C to 250°C, and a heating rate of 5°C / min. The peak top temperature of Tan δ was recorded as Tg. The obtained Tg was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: Tg was 120°C or higher. B: Tg was 100°C or higher but less than 120°C. C: Tg was 80°C or higher but less than 100°C. D: Tg was less than 80°C.

[0196] [Reaction Rate When Cured at 165°C] The reaction rate when the epoxy resin composition was cured at 165°C was measured by the following method. Using an EXSTER6000 (Hitachi High-Tech Science Corporation), the temperature was raised from 25°C to 300°C at a rate of 5°C / min, and the total amount of heat generated in the temperature range from 100°C to 250°C was calculated. Furthermore, for Examples 1-1 to 1-11 and Comparative Example 1-1, measurements were similarly taken after placing the samples in a small high-temperature chamber (manufactured by Espec Corporation) at 180°C for 2 hours, and the change in heat generated in the same temperature range was calculated as a percentage. Furthermore, for Examples 1-12 to 1-14, measurements were similarly taken after placing the samples in a small high-temperature chamber (manufactured by Espec Corporation) at 165°C for 2 hours, and the change in heat generated in the same temperature range was calculated as a percentage. The calculation formula is as follows: Initial heat release A: DSC peak heat release of the compound Post-cure heat release B: DSC peak heat release of the compound after heating Reaction rate (%) = 100 x (initial heat release A - post-cure heat release B) / initial heat release A The obtained reaction rate was evaluated according to the following evaluation criteria. [Evaluation criteria] A: The reaction rate was 90% or more. B: The reaction rate was less than 90% and 80% or more. C: The reaction rate was less than 80% and 70% or more. D: The reaction rate was less than 70%.

[0197] The abbreviations for the components in this example have the following meanings: (Aromatic amines (A-1)) APAB: 4-aminophenyl-4'-aminobenzoate 44DAS: 4,4'-diaminodiphenyl sulfone 34ODA: 3,4'-diaminodiphenyl ether TPE-M: 1,3-bis(3-aminophenoxy)benzene m-TB: m-tolidine Ethacure 300: curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Ethacure 100 Plus (+): curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Kayahard AA: curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.)

[0198] (Reactive compounds) 2-EH: 2-ethylhexyl glycidyl ether BGE: butyl glycidyl ether ph-GE: phenyl glycidyl ether

[0199] (Epoxy resin) EXA-850CRP (manufactured by DIC Corporation) EXA-830CRP (manufactured by DIC Corporation) JER-630LSD (manufactured by Mitsubishi Chemical Corporation)

[0200] (Curing accelerator) 2P4MHZ-PW (manufactured by Shikoku Chemicals Corporation)

[0201] (Inorganic filler) SE203G-SEJ (manufactured by Admatechs Co., Ltd.)

[0202] <Preparation of Epoxy Resin Curing Agent> (Synthesis Example 1-1) After replacing the atmosphere in a 500 ml four-neck flask equipped with a reflux condenser and a stirring blade with nitrogen, 20 g of 1-butanol and 0.05 mol of 3,4'-oxydianiline (34ODA) were added and the flask was heated until the internal temperature reached 120°C. Then, using a dropping funnel, 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was added dropwise over 30 minutes. After the dropwise addition was completed, the reaction solution was stirred while being heated at 120°C for 6 hours to complete the reaction. Using an evaporator, the 1-butanol was distilled off from the resulting solution over 2 hours while maintaining the temperature at 80°C and the pressure at 15 mmHg or less, yielding epoxy resin curing agent (A-1). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement. The results are shown in Table 3.

[0203] Synthesis Example 1-2: An epoxy resin curing agent (A-2) was obtained in the same manner as in Synthesis Example 1-1, except that 2-EH was changed to butyl glycidyl ether (BGE). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0204] Synthesis Example 1-3: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was changed to 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an epoxy resin curing agent (B). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0205] Synthesis Example 1-4: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was changed to 4-aminophenyl-4'-aminobenzoate (APAB), to obtain an epoxy resin curing agent (C-1). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0206] Synthesis Example 1-5: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-4, except that 2-ethylhexyl glycidyl ether was changed to butyl glycidyl ether, to obtain an epoxy resin curing agent (C-2). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0207] Synthesis Example 1-6: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was changed to m-tolidine (m-TB), to obtain an epoxy resin curing agent (D). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0208] Synthesis Example 1-7: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was changed to Kayahard AA, to obtain an epoxy resin curing agent (E-1). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0209] Synthesis Example 1-8: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-7, except that 2-ethylhexyl glycidyl ether was changed to butyl glycidyl ether, to obtain an epoxy resin curing agent (E-2). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0210] Synthesis Example 1-9: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was replaced with Ethacure 100 Plus, to obtain an epoxy resin curing agent (F-1). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0211] Synthesis Example 1-10: Synthesis and purification were performed under the same conditions as in Synthesis Example 1-9, except that 2-ethylhexyl glycidyl ether was changed to phenyl glycidyl ether, to obtain an epoxy resin curing agent (F-2). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0212] Synthesis Example 1-11 Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was changed to DMTDA, to obtain an epoxy resin curing agent (G). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0213] Synthesis Example 1-12: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-4, except that the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.03 mol, to obtain an epoxy resin curing agent (C-3). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0214] Synthesis Example 1-13: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-5, except that the amount of butyl glycidyl ether was changed from 0.05 mol to 0.035 mol, to obtain an epoxy resin curing agent (C-4). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0215] Synthesis Example 1-14: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-7, except that the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.025 mol, to obtain an epoxy resin curing agent (E-3). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0216] Synthesis Example 1-15: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-8, except that the amount of phenyl glycidyl ether was changed from 0.05 mol to 0.04 mol, to obtain an epoxy resin curing agent (E-4). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0217] Synthesis Example 1-16: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-9, except that the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.025 mol, to obtain an epoxy resin curing agent (F-3). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0218] Synthesis Example 1-17: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-9, except that the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.03 mol of butyl glycidyl ether, to obtain an epoxy resin curing agent (F-4). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0219]

[0220] <Preparation of Epoxy Resin Composition> (Synthesis of Compound (Mixture Containing Compounds D-1A and D-1B)) 7.20 g (0.07 mol) of ethyl propionate, 13.17 g (0.0245 mol) of Denacol EX-830, and 1.67 g (0.0105 mol) of EX-830CRP were weighed into a recovery flask, and the flask was heated to 90°C in an oil bath. Next, 6.00 g (0.06 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound A [a mixture containing compounds (D-1A) and (D-1B)] as a liquid product. Compounds (D-1A) and (D-1B) correspond to compounds represented by formula (6). The structures of compounds (D-1A) and (D-1B) are as follows:

[0221]

[0222] (Synthesis of Compound (D-1C)) 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of butyl glycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90°C. Next, 3.85 g (0.038 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After completion of the addition, the reaction was continued for 4 hours while stirring while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound (D-1C) as a liquid product. Compound (D-1C) corresponds to the compound represented by formula (4). The structure of Compound (D-1C) is as follows:

[0223]

[0224] (Synthesis of Compound (D-1D)) 1.94 g (0.019 mol) of ethyl propionate and 5.00 g (0.009 mol) of polyethylene glycol diglycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90°C. Next, 1.62 g (0.016 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After completion of the addition, the reaction was continued for 4 hours while stirring while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound (D-1D) as a liquid product. Compound (D-1D) corresponds to the compound represented by formula (6). The structure of Compound (D-1D) is shown below.

[0225]

[0226] (Examples 1-1 to 1-11, Examples 1-15 to 1-20, Comparative Example 1-1) Each of the components shown in Tables 4 to 6 was placed in a plastic stirring vessel in the amounts shown in Tables 4 to 6, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition. The resulting epoxy resin composition was poured into a Teflon (registered trademark) metal frame and heated at 180°C for 2 hours to produce a cured product. The Tg of the resulting cured product was evaluated.

[0227] (Examples 1-12 to 1-14, Examples 1-21 to 1-24, Comparative Example 1-1) Each of the components shown in Tables 4 to 6 was placed in a plastic stirring vessel in the amounts shown in Tables 4 to 6, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition. The resulting epoxy resin composition was poured into a Teflon metal frame and heated at 165°C for 2 hours to produce a cured product. The Tg of the resulting cured product was evaluated.

[0228]

[0229]

[0230]

[0231] As shown in Tables 4 to 6, the examples using epoxy resin curing agents containing an aromatic amine compound (A-1) represented by Formula (1), the following Formula (2), or the following Formula (3), and an aromatic amine adduct (A-2), which is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group reactive with the aromatic amine compound (A-1), exhibited excellent flow properties, curing properties, and storage stability. Therefore, the epoxy resin curing agents of the examples exhibited excellent penetration properties and were able to achieve both curing properties and storage stability. Comparative Example 1-1, which did not use the aromatic amine adduct (A-2), which is a reaction product of the aromatic amine compound (A-1) and a reactive compound, exhibited poor flow properties and therefore poor penetration properties. The reason for this is presumably that the epoxy resin composition described in Comparative Example 1-1 did not contain the aromatic amine adduct (A-2), and therefore had poor viscosity stability.

[0232] Furthermore, it was confirmed that the epoxy resin compositions described in Examples 1-12 to 1-14 and 1-21 to 1-24 had sufficient curability even when the temperature was lowered from 180°C to 165°C by adding a curing accelerator (curing catalyst) to compensate for the reactivity of the amine adduct. The epoxy resin compositions of the examples can be suitably used as encapsulants, particularly underfill materials used for encapsulating semiconductor chips and the like.

[0233] When the aromatic amine compound (A-1) represented by Formula (1), Formula (2), or Formula (3) is not used, the epoxy resin composition exhibits poor flowability and therefore poor penetration. In the above cases, the Tg and Tm of the epoxy resin curing agent are relatively high, resulting in poor viscosity when formed into an epoxy resin composition, and as a result, poor flowability. When an aromatic amine compound other than the aromatic amine compound (A-1) of the first embodiment is used, the epoxy resin composition exhibits excellent viscosity stability but poor curability and a low Tg. This is because, for example, the use of an amine having an electron-withdrawing group such as a sulfonyl group (e.g., 4,4'-diaminodiphenyl sulfone) as the aromatic amine compound reduces reactivity and compatibility with the epoxy resin. Furthermore, when an aromatic amine compound other than the aromatic amine compound (A-1) of the first embodiment is used, the epoxy resin composition exhibits low viscosity but poor viscosity stability and may exhibit poor flowability. The reason for this is that, for example, when an aromatic amine compound having a functional group such as a methylene group and no substituent on the side chain (4,4'-diaminodiphenylmethane, etc.) is used as the aromatic amine compound, the reactivity of the aromatic amine compound used is too high.

[0234] The second embodiment will be described below with specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. In other words, a person skilled in the art can practice the present invention by making various modifications to the examples shown below. In the following, unless otherwise specified, "parts" are based on mass.

[0235] [Analysis of Components in Epoxy Resin Curing Agent] Analysis was carried out by the method described in the above section [Analysis of Components in Epoxy Resin Curing Agent].

[0236] [Method for measuring glass transition temperature (Tg) and melting point (Tm) of epoxy resin curing agent] The glass transition temperature (Tg) and melting point (Tm) of the epoxy resin curing agent were measured using a differential scanning calorimeter (differential scanning calorimetry system, "DSC Q2000", manufactured by TA Instruments-Waters Corporation) under a nitrogen gas flow (40 mL / min) by heating a 10 mg sample from -50°C to 200°C at a heating rate of 5°C / min. The Tm of the amine adduct was taken as the apex temperature of the endothermic peak in the DSC curve (JIS K7121-1987), and the Tg was taken as the peak top temperature of the DSC differential curve (Reference: JIS K6240). The obtained Tg and Tm were evaluated according to the following evaluation criteria. [Evaluation criteria for Tg] A: Tg was -20°C or lower. B: Tg was greater than -20°C and less than 5°C. C: Tg was more than 5 and not more than 20°C. D: Tg was above 20°C. [Evaluation criteria for Tm] A: No clear peak top temperature was observed. B: Tm was not less than -20°C and less than 20°C. C: Tm was not less than 20°C and not more than 60°C. D: Tm was above 60°C.

[0237] [Method for measuring viscosity of epoxy resin composition at 25°C] The viscosity (Pa s) of the epoxy resin composition at 25°C was measured using an E-type viscometer (TV-20, manufactured by Toki Sangyo Co., Ltd.) 5 minutes after the resin composition (0.3 mL) was dropped into a measuring cup and the sample temperature reached 25°C (cone No. 5, 3°, R=12 mm). The obtained viscosity was evaluated according to the following evaluation criteria. [Evaluation criteria] A: The viscosity at 25°C was less than 10 Pa s. B: The viscosity at 25°C was 10 Pa s or more and less than 50 Pa s. C: The viscosity at 25°C was 50 Pa s or more and less than 100 Pa s. D: The viscosity at 25°C was 100 Pa s or more.

[0238] [Method for measuring viscosity of epoxy resin composition at 110°C] The viscosity (Pa s) of the epoxy resin composition at 110°C was measured using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) by dropping 0.2 mL of the resin composition onto a measurement plate and measuring the viscosity 5 minutes after the sample temperature reached 110°C (aluminum cone plate R=20 mm, shear rate 20 ( / sec). The obtained viscosity was evaluated according to the following evaluation criteria. [Evaluation criteria] A: The viscosity at 110°C was less than 0.10 Pa s. B: The viscosity at 110°C was 0.10 Pa s or more and less than 0.20 Pa s. C: The viscosity at 110°C was 0.20 Pa s or more and less than 0.50 Pa s. D: The viscosity at 110°C was 0.50 or more.

[0239] [Method for Evaluating Viscosity Stability at 110°C (High Temperature)] The viscosity stability of the epoxy resin composition at 110°C was evaluated by dropping 0.2 mL of the resin composition onto a measurement plate, and measuring the viscosity using a rheometer (HAAKE MARS, manufactured by Thermo Scientific) 5 minutes and 60 minutes after the sample temperature reached 110°C (aluminum parallel plate R=20 mm, shear rate 20 ( / sec)). The viscosity after 5 minutes was defined as "η1" and the viscosity after 60 minutes as "η2," and the value calculated by η2 / η1 was determined as the viscosity increase ratio. The obtained viscosity increase ratios were evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The viscosity increase ratio was less than 3.0 times. B: The viscosity increase ratio was 3.0 times or more and less than 10.0 times. C: The viscosity increase ratio was 10.0 times or more and less than 40.0 times. D: The viscosity increase ratio was 40.0 times or more.

[0240] [Evaluation of Flow Properties] A test specimen was prepared by fixing a glass plate instead of a semiconductor element on a glass substrate (26 mm wide x 75 mm long) with a gap of 25 μm. Next, this test specimen was placed on a hot plate set at 110° C., and an epoxy resin composition was applied to one end of the glass plate. The time (seconds) required for the resin to pass through the gap and reach a point 20 mm away was measured. The obtained time was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The arrival time was less than 80 seconds. B: The arrival time was 80 seconds or more but less than 120 seconds. C: The arrival time was 120 seconds or more but less than 200 seconds. D: The arrival time was 200 seconds or more.

[0241] [Method for Measuring Tg of Cured Product] Epoxy resin compositions were cured at 165°C (180°C when no amine imide was included) for 2 hours to prepare test specimens (2 mm thick x 20 mm long x 10 mm wide). The test specimens were measured using a thermomechanical analyzer (RSA-G2, manufactured by TA Instruments Japan, Inc.) in Force Tracking mode under conditions of an initial load of 0.5 N, a measurement temperature of 0°C to 250°C, and a heating rate of 5°C / min. The peak top temperature of Tan δ was recorded as Tg. The obtained Tg was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: Tg was 120°C or higher. B: Tg was 100°C or higher but less than 120°C. C: Tg was 80°C or higher but less than 100°C. D: Tg was less than 80°C.

[0242] [Reaction Rate When Cured at 165°C] The reaction rate when the epoxy resin composition was cured at 165°C was measured by the following method. Using an EXSTER6000 (Hitachi High-Tech Science Corporation), the temperature was raised from 25°C to 300°C at a rate of 5°C / min, and the total amount of heat generated in the temperature range from 100°C to 250°C was calculated. Furthermore, for Examples 1-1 to 1-11, 1-15 to 1-24, and Comparative Example 1-1, measurements were also taken in a small high-temperature chamber (manufactured by Espec Corporation) at 180°C for 2 hours, and the change in heat generated in the same temperature range was calculated as a percentage. Furthermore, for Examples 1-12 to 1-14, measurements were also taken in a small high-temperature chamber (manufactured by Espec Corporation) at 165°C for 2 hours, and the change in heat generated in the same temperature range was calculated as a percentage. The calculation formula is as follows: Initial heat release A: DSC peak heat release of the compound Post-cure heat release B: DSC peak heat release of the compound after heating Reaction rate (%) = 100 x (initial heat release A - post-cure heat release B) / initial heat release A The obtained reaction rate was evaluated according to the following evaluation criteria. [Evaluation criteria] A: The reaction rate was 90% or more. B: The reaction rate was less than 90% and 80% or more. C: The reaction rate was less than 80% and 70% or more. D: The reaction rate was less than 70%.

[0243] The abbreviations for the components in this example have the following meanings: (Aromatic amine (A-1)) APAB: 4-aminophenyl-4'-aminobenzoate 34ODA: 3,4'-diaminodiphenyl ether (Tg: room temperature (20°C) or higher) (Tm: 74°C) TPE-M: 1,3-bis(3-aminophenoxy)benzene m-TB: m-tolidine Ethacure 300: curing agent containing diethylthiotoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Ethacure 100 Plus (+): curing agent containing diethyltoluenediamine (manufactured by Mitsui Fine Chemicals, Inc.) Kayahard AA: curing agent containing 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd.) 44DAS: 4,4'-diaminodiphenyl sulfone

[0244] (Reactive compounds) 2-EH: 2-ethylhexyl glycidyl ether BGE: butyl glycidyl ether ph-GE: phenyl glycidyl ether 1-BH: 1-bromohexane

[0245] (Epoxy resin) EXA-850CRP (manufactured by DIC Corporation) EXA-830CRP (manufactured by DIC Corporation) JER-630LSD (manufactured by Mitsubishi Chemical Corporation)

[0246] (Curing accelerator) 2P4MHZ-PW (manufactured by Shikoku Chemicals Corporation)

[0247] (Inorganic filler) SE203G-SEJ (manufactured by Admatechs Co., Ltd.)

[0248] <Preparation of epoxy resin curing agent>

[0249] (Synthesis Example 1-1) An epoxy resin curing agent (A-2) was obtained in the same manner as in Synthesis Example 1-1, except that 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.055 mol of butyl glycidyl ether (BGE). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0250] Synthesis Example 1-2: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 0.05 mol of 3,4'-oxydianiline (34ODA) was changed to 0.055 mol of 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an epoxy resin curing agent (B). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0251] Synthesis Example 1-3: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-4, except that 2-ethylhexyl glycidyl ether (2-EH) was replaced with 0.06 mol of butyl glycidyl ether (BGE), to obtain an epoxy resin curing agent (C-2). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0252] (Synthesis Example 1-4) Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was changed to m-tolidine (m-TB) and the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.075 mol, to obtain an epoxy resin curing agent (D). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0253] Synthesis Example 1-5: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-7, except that 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.065 mol of phenyl glycidyl ether (ph-GE), to obtain an epoxy resin curing agent (E-2). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0254] Synthesis Example 1-6: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-9, except that 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.060 mol of phenyl glycidyl ether (ph-GE), to obtain an epoxy resin curing agent (F-2). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0255] Synthesis Example 1-7: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 3,4'-oxydianiline (34ODA) was changed to Ethacure 300 and the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.055 mol, to obtain an epoxy resin curing agent (G). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0256] Synthesis Example 1-8: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-4, except that the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.75 mol, to obtain an epoxy resin curing agent (C-3). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0257] Synthesis Example 1-9: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-5, except that the amount of butyl glycidyl ether (BGE) was changed from 0.05 mol to 0.075 mol, to obtain an epoxy resin curing agent (C-4). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0258] Synthesis Example 1-10: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-7, except that the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.03 mol, to obtain an epoxy resin curing agent (E-3). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0259] Synthesis Example 1-11: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-8, except that the amount of phenyl glycidyl ether (ph-GE) was changed from 0.05 mol to 0.035 mol, to obtain an epoxy resin curing agent (E-4). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0260] Synthesis Example 1-12: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-9, except that the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.025 mol, to obtain an epoxy resin curing agent (F-3). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0261] Synthesis Example 1-13: Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-9, except that the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.035 mol of butyl glycidyl ether (BGE), to obtain an epoxy resin curing agent (F-4). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0262] Synthesis Example 1-14 After a 500 ml four-neck flask equipped with a reflux condenser and a stirring blade was purged with nitrogen, 7.5 g of 1-butanol and 0.02 mol of 4,4'-diaminodiphenyl sulfone (44DAS) were added and heated until the internal temperature reached 120°C. Then, using a dropping funnel, 0.02 mol of 1-bromohexane (1-BH) was added dropwise over 30 minutes. After the dropwise addition was completed, the reaction solution was stirred while being heated at 120°C for 24 hours to complete the reaction. Using an evaporator, the 1-butanol was distilled off from the resulting solution over 2 hours while maintaining the temperature at 80°C and the pressure at 15 mmHg or less, yielding an epoxy resin curing agent (A-1). The ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC / MS measurement.

[0263]

[0264] <Preparation of Epoxy Resin Composition> (Synthesis of Compound (Mixture Containing Compounds D-1A and D-1B)) 7.20 g (0.07 mol) of ethyl propionate, 13.17 g (0.0245 mol) of Denacol EX-830, and 1.67 g (0.0105 mol) of EX-830CRP were weighed into a recovery flask, and the flask was heated to 90°C in an oil bath. Next, 6.00 g (0.06 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound A [a mixture containing compounds (D-1A) and (D-1B)] as a liquid product. The structures of compounds (D-1A) and (D-1B) are as follows:

[0265]

[0266] (Synthesis of Compound (D-1C)) 3.93 g (0.038 mol) of ethyl propionate and 5.00 g (0.038 mol) of butyl glycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90°C. Next, 3.85 g (0.038 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound (D-1C) as a liquid product. The structure of Compound (D-1C) is shown below.

[0267]

[0268] (Synthesis of Compound (D-1D)) 1.94 g (0.019 mol) of ethyl propionate and 5.00 g (0.009 mol) of polyethylene glycol diglycidyl ether were weighed into a recovery flask, and the flask was heated in an oil bath to 90°C. Next, 1.62 g (0.016 mol) of 1-aminopiperidine was added dropwise over 15 minutes. After completion of the addition, the mixture was stirred for 4 hours while maintaining the temperature at 90°C, and the reaction was completed. The resulting reaction solution was concentrated under reduced pressure at 80°C to remove the by-product alcohol and unreacted raw materials, yielding Compound (D-1D) as a liquid product. The structure of Compound (D-1D) is shown below.

[0269]

[0270] (Examples 1-1 to 1-7, Examples 1-11 to 1-17, Comparative Example 1-1) Each of the components shown in Tables 8 to 10 was placed in a plastic stirring vessel in the amounts shown in Tables 8 to 10, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition. The resulting epoxy resin composition was poured into a Teflon (registered trademark) metal frame and heated at 180°C for 2 hours to produce a cured product. The Tg of the resulting cured product was evaluated.

[0271] (Examples 1-8 to 1-10, Examples 1-18 to 1-20) Each of the components shown in Tables 8 to 10 was placed in a plastic stirring vessel in the amounts shown in Tables 8 to 10, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition. The resulting epoxy resin composition was poured into a Teflon metal frame and heated at 165°C for 2 hours to produce a cured product. The Tg of the resulting cured product was evaluated.

[0272]

[0273]

[0274]

[0275] As shown in Tables 8 to 10, the examples using epoxy resin curing agents containing an aromatic amine compound (A-1) and an aromatic amine adduct (A-2), which is a reaction product of the aromatic amine compound and a reactive compound having a functional group reactive with the aromatic amine compound, and having a glass transition temperature (Tg) of 20°C or less as detected by differential scanning calorimetry (DSC) at a heating rate of 5°C / min, exhibited excellent flow properties, curing properties, and storage stability. Therefore, the epoxy resin curing agents of the examples exhibited excellent permeability and were able to achieve both curing properties and storage stability. Comparative Example 1-1, which used a curing agent whose glass transition temperature (Tg) as detected by differential scanning calorimetry (DSC) at a heating rate of more than 20°C or less, exhibited poor flow properties and therefore poor permeability. This is thought to be due to poor affinity with the epoxy resin, which resulted in poor viscosity when formed into an epoxy resin composition, resulting in reduced flow properties.

[0276] Furthermore, it was confirmed that the epoxy resin compositions described in Examples 1-8 to 1-10 and 1-18 to 1-20 had sufficient curability even when the temperature was lowered from 180°C to 165°C by adding a curing catalyst to compensate for the reactivity of the amine adduct. The epoxy resin compositions of the examples can be suitably used as encapsulants, particularly underfill materials used for encapsulating semiconductor chips and the like.

[0277] When an epoxy resin curing agent having a glass transition temperature (Tg) of more than 20°C or less is used, the flowability is poor and therefore the penetration is poor. In the above cases, the Tg and Tm of the epoxy resin curing agent are relatively high, so the viscosity as a curing agent is high and the affinity with epoxy resins is poor, resulting in poor viscosity when formed into an epoxy resin composition, and as a result, poor flowability. When an epoxy resin curing agent having a glass transition temperature (Tg) of more than 20°C or less is used, the reactivity as a curing agent is excellent, but the viscosity as a curing agent is high and the affinity with epoxy resins is poor, resulting in poor curing when formed into an epoxy resin composition, and the reaction does not proceed sufficiently even after thermal curing, resulting in a low Tg.

[0278] The first embodiment of this embodiment also includes the following aspects: <1> An epoxy resin curing agent comprising: an aromatic amine compound (A-1) represented by the following formula (1), (2), or (3), and an aromatic amine adduct (A-2) that is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).

[0279]

[0280] In formula (1), R α and R β each independently represents 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 having one or more aromatic rings, or -O-, -CO-, -C(=O)O-, or -C(=O)NH-.

[0281]

[0282] In formula (2), R γ and R δ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; c and d each independently represent an integer of 1 to 4; and Y represents a divalent organic group or a single bond.

[0283]

[0284] In formula (3), R εrepresents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and e is an integer of 1 to 4. <2> The epoxy resin curing agent according to <1>, which has a glass transition temperature (Tg) of 10°C or lower as detected by differential scanning calorimetry (DSC) measured at a heating rate of 5°C / min. <3> The epoxy resin curing agent according to <1> or <2>, which has at least one melting point (Tm) of 60°C or lower as detected by differential scanning calorimetry (DSC) measured at a heating rate of 5°C / min. <4> The epoxy resin curing agent according to any one of <1> to <3>, which has no melting point (Tm) detected in the range of -20°C to 60°C in differential scanning calorimetry (DSC) measured at a heating rate of 5°C / min in the temperature range of -50°C to 200°C. <5> The epoxy resin curing agent according to any one of <1> to <4>, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1), obtained by liquid chromatography analysis (UV detector), is 0.10 to 0.45. <6> The epoxy resin curing agent according to any one of <1> to <5>, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.5 to 2.0. <7> The epoxy resin curing agent according to any one of <1> to <6>, wherein the reactive compound is a compound having one glycidyl group in the molecule. <8> An epoxy resin composition comprising the epoxy resin curing agent according to any one of <1> to <7>, an epoxy resin (B), and an inorganic filler (C). <9> The epoxy resin composition according to <8>, further comprising a curing accelerator (D).<10> The epoxy resin composition according to <9>, wherein the curing accelerator (D) is at least one selected from the group consisting of a compound (D-1) represented by the following formula (4), the following formula (5), or the following formula (6), and an imidazole-based compound (D-2):

[0285]

[0286]

[0287]

[0288] (In formulas (4) to (6), R １ each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. ５ represents a negatively charged nitrogen atom, R ６represents a positively charged nitrogen atom.) <11> The epoxy resin composition according to any one of <8> to <10>, wherein the content of the inorganic filler (C) is 40% by mass to 70% by mass, based on the total amount of the epoxy resin composition. <12> The epoxy resin composition according to any one of <8> to <11>, wherein the viscosity (η2) after standing at 110°C for 60 minutes is 0.01 Pa s to 1.50 Pa s. <13> The epoxy resin composition according to <12>, wherein the ratio (thickness increase rate, η2 / η1) of the viscosity (η2) after standing at 110°C for 60 minutes to the viscosity (η1) after standing at 110°C for 5 minutes is 1.0 to 40.0 times, and wherein the reaction rate when cured at 165°C is 80% to 99%. <14> A cured product of the epoxy resin composition according to any one of <8> to <13>. <15> An encapsulant comprising the cured product according to <14>. <16> The encapsulant according to <15>, which is an encapsulant for semiconductors. <17> An adhesive comprising the epoxy resin composition according to any one of <8> to <13>. <18> A semiconductor package comprising the cured product according to <14>. <19> A method for producing a semiconductor package, comprising a step of producing a semiconductor package using the epoxy resin composition according to any one of <8> to <13>.

[0289] A second embodiment of this embodiment also includes the following aspects. <1> An epoxy resin curing agent comprising an aromatic amine compound (A-1) and an aromatic amine adduct (A-2) that is a reaction product of the aromatic amine compound and a reactive compound having a functional group reactive with the aromatic amine compound, wherein the curing agent has a glass transition temperature (Tg) of 5°C or lower as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5°C / min. <2> The epoxy resin curing agent according to <1>, wherein the curing agent has no melting point (Tm) in the range of -20°C to 60°C as detected by differential scanning calorimetry (DSC analysis) measured at a temperature range of -50°C to 200°C and a heating rate of 5°C / min. <3> The epoxy resin curing agent according to <1> or <2>, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1), as determined by liquid chromatography analysis (UV detector), is 0.10 to 0.45. <4> The epoxy resin curing agent according to any one of <1> to <3>, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.50 to 2.00. <5> The epoxy resin curing agent according to any one of <1> to <4>, wherein the glass transition temperature (Tg) detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5°C / min is -20°C or lower. <6> The epoxy resin curing agent according to any one of <1> to <5>, wherein the aromatic amine compound (A-1) is an aromatic amine compound represented by the following formula (1) or (2):

[0290]

[0291] In formula (1), R α and R βeach independently represents 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.

[0292]

[0293] In formula (2), R γ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and c is an integer of 1 to 4. <7> The epoxy resin curing agent according to any one of <1> to <6>, wherein the reactive compound is an epoxy compound having one glycidyl group in the molecule. <8> An epoxy resin composition comprising the epoxy resin curing agent according to any one of <1> to <7>, an epoxy resin (B), and an inorganic filler (C). <9> The epoxy resin composition according to <8>, further comprising a curing accelerator (D). <10> The epoxy resin composition according to <8> or <9>, wherein the curing accelerator is at least one selected from the group consisting of a compound (D-1) represented by the following formula (4), the following formula (5), or the following formula (6), and an imidazole-based compound (D-2).

[0294]

[0295]

[0296]

[0297] (In formulas (4) to (6), R １ each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. ５ represents a negatively charged nitrogen atom, R ６represents a positively charged nitrogen atom.) <11> The epoxy resin composition according to any one of <8> to <10>, wherein the content of the inorganic filler (C) is 50% by mass to 70% by mass, based on the total amount of the epoxy resin composition. <12> The epoxy resin composition according to any one of <8> to <11>, wherein the viscosity after standing at 110°C for 60 minutes is 0.01 Pa·s to 1.50 Pa·s. <13> The epoxy resin composition according to <12>, wherein the viscosity increase rate after standing at 110°C for 60 minutes is 1.0 to 40.0 times, and the conversion rate when cured at 165°C is 80 to 99%. <14> The epoxy resin composition according to any one of <8> to <13>, wherein the viscosity at 25°C is 50 Pa·s or less. <15> A cured product of the epoxy resin composition according to any one of <8> to <14>. <16> An encapsulant comprising the cured product according to <15>. <17> The encapsulant according to <16>, which is an encapsulant for semiconductors. <18> An adhesive comprising the epoxy resin composition according to any one of <8> to <14>. <19> A semiconductor package comprising the cured product according to <15>. <20> A method for producing a semiconductor package, comprising a step of producing a semiconductor package using the epoxy resin composition according to <14>.

[0298] The disclosures of Japanese Patent Application Nos. 2023-125550, filed on August 1, 2023, and 2023-125565, filed on August 1, 2023, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. An epoxy resin curing agent comprising: an aromatic amine compound (A-1) represented by the following formula (1), (2) or (3); and an aromatic amine adduct (A-2) which is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1). In formula (1), R α and R β each independently represents 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; X represents a divalent organic group having one or more aromatic rings, or -O-, -CO-, -C(=O)O-, -SO ２ -, or -C(=O)NH-. In formula (2), R γ and R δ each independently represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; c and d each independently represent an integer of 1 to 4; and Y represents a divalent organic group or a single bond. In formula (3), R ε represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.

2. The epoxy resin curing agent according to claim 1, which has a glass transition temperature (Tg) of 10°C or lower as detected by differential scanning calorimetry (DSC analysis) measured at a heating rate of 5°C / min.

3. The epoxy resin curing agent according to claim 1, which has at least one melting point (Tm) of 60°C or lower as detected by differential scanning calorimetry (DSC analysis) measured at a heating rate of 5°C / min.

4. An epoxy resin curing agent comprising: an aromatic amine compound (A-1); and an aromatic amine adduct (A-2) which is a reaction product of the aromatic amine compound and a reactive compound having a functional group capable of reacting with the aromatic amine compound, the glass transition temperature (Tg) being 20°C or lower as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5°C / min.

5. The epoxy resin curing agent according to claim 4, which has a glass transition temperature (Tg) of 5°C or less as detected by differential scanning calorimetry (DSC) at a heating rate of 5°C / min.

6. The epoxy resin curing agent according to claim 4, which has a glass transition temperature (Tg) of -20°C or lower as detected by differential scanning calorimetry (DSC) at a heating rate of 5°C / min.

7. The epoxy resin curing agent according to claim 4, wherein the aromatic amine compound (A-1) is an aromatic amine compound represented by the following formula (1) or (2): In formula (1), R α and R β each independently represents 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. In formula (2), R γ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and c is an integer of 1 to 4.

8. The epoxy resin curing agent according to claim 1 or 2, which has no detectable melting point (Tm) in the range of -20°C to 60°C in differential scanning calorimetry (DSC analysis) measured in the temperature range of -50°C to 200°C at a heating rate of 5°C / min.

9. The epoxy resin curing agent according to claim 1 or 2, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.10 to 0.

45.

10. The epoxy resin curing agent according to claim 1 or 2, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1 / A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.5 to 2.

0.

11. The epoxy resin curing agent according to claim 1 or 2, wherein the reactive compound is a compound having one glycidyl group in the molecule.

12. An epoxy resin composition comprising the epoxy resin curing agent according to claim 1 or 2, an epoxy resin (B), and an inorganic filler (C).

13. The epoxy resin composition according to claim 12, further comprising a curing accelerator (D).

14. The epoxy resin composition according to claim 13, wherein the curing accelerator (D) is at least one selected from the group consisting of a compound (D-1) represented by the following formula (4), (5), or (6), and an imidazole-based compound (D-2): (In formulas (4) to (6), R １ each independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond; R ２ and R ３ each independently represents an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combines to form a heterocycle having 7 or less carbon atoms; R ４ R each independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom; n represents an integer of 1 to 3. ５ represents a negatively charged nitrogen atom, R ６ represents a positively charged nitrogen atom.) 15. The epoxy resin composition according to claim 12, wherein the content of the inorganic filler (C) is 40% by mass to 70% by mass, based on the total amount of the epoxy resin composition.

16. The epoxy resin composition according to claim 12, which has a viscosity (η2) of 0.01 Pa·s to 1.50 Pa·s after standing at 110° C. for 60 minutes.

17. The epoxy resin composition according to claim 16, in which the ratio (η2) of the viscosity after standing at 110°C for 60 minutes to the viscosity (η1) after standing at 110°C for 5 minutes (thickening rate, η2 / η1) is 1.0 to 40.0 times, and the reaction rate when cured at 165°C is 80% to 99%.

18. The epoxy resin composition according to claim 12, having a viscosity at 25°C of 50 Pa·s or less.

19. A cured product of the epoxy resin composition according to claim 12.

20. A sealing material comprising the cured product according to claim 19.

21. The encapsulant according to claim 20, which is an encapsulant for semiconductors.

22. An adhesive comprising the epoxy resin composition of claim 12.

23. A semiconductor package comprising the cured product according to claim 19.

24. A method for producing a semiconductor package, comprising the step of producing a semiconductor package using the epoxy resin composition according to claim 12.

Images