WO2025028605A1 - 硬化剤、エポキシ樹脂組成物、硬化物、封止材及び接着剤 - Google Patents

硬化剤、エポキシ樹脂組成物、硬化物、封止材及び接着剤 Download PDF

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Publication number
WO2025028605A1
WO2025028605A1 PCT/JP2024/027515 JP2024027515W WO2025028605A1 WO 2025028605 A1 WO2025028605 A1 WO 2025028605A1 JP 2024027515 W JP2024027515 W JP 2024027515W WO 2025028605 A1 WO2025028605 A1 WO 2025028605A1
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Prior art keywords
epoxy resin
group
curing agent
resin composition
compound
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PCT/JP2024/027515
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English (en)
French (fr)
Japanese (ja)
Inventor
凌輔 岡本
直弥 上村
聡 加藤
雄太 佐藤
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to JP2025537500A priority Critical patent/JPWO2025028605A1/ja
Priority to KR1020257040808A priority patent/KR20260006012A/ko
Priority to CN202480040108.5A priority patent/CN121420012A/zh
Publication of WO2025028605A1 publication Critical patent/WO2025028605A1/ja
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W74/00—Encapsulations, e.g. protective coatings
    • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
    • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
    • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler

Definitions

  • the present invention relates to a curing agent, an epoxy resin composition, a cured product, a sealant, and an adhesive.
  • Epoxy resins are used in a wide range of applications, including paints, electrical and electronic insulating materials, and adhesives, because the cured products have excellent mechanical, electrical, and thermal properties, as well as chemical resistance and adhesive properties.
  • JP 2012-175009 A JP 2015-507360 A JP 2016-58627 A JP 2014-197675 A
  • thermosetting resin composition thermosetting adhesive
  • the thermosetting resin composition does not penetrate sufficiently into the gap due to its low high-temperature stability, making it difficult to completely fill the gap, and there are still issues with injectability into large areas.
  • NCF Non-Conductive Film
  • the problem to be solved by the first embodiment of the present invention is to provide a curing agent, an epoxy resin composition, a cured product, a sealant, and an adhesive that have excellent heat resistance when made into a resin cured product, and also have excellent high-temperature stability when made into a resin composition.
  • the problem to be solved by the second embodiment of the present invention is to provide an epoxy resin composition, a cured product, a sealant, and an adhesive that are excellent in reliability and injectability into a large area.
  • This embodiment includes the first and second embodiments.
  • the first embodiment of the present invention includes the following ⁇ 1> and items quoting ⁇ 1>.
  • the second embodiment of this embodiment includes the following ⁇ 12> and items citing ⁇ 12>.
  • ⁇ 1> (A) a compound having a nitrogen functional group, (B) at least one compound selected from the group consisting of compounds represented by the following formula (1), the following formula (2), and the following formula (3),
  • a hardener comprising:
  • R 1 's each independently represent 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 represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle having 7 or less carbon atoms
  • R 4 's each independently represent 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
  • R 5 represents a negatively charged nitrogen atom
  • R 6 represents a positively charged nitrogen atom.
  • R 1 to R 3 each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may have a nitrogen atom, an oxygen atom, a hydroxyl group, an amino group, a phenyl group, a sulfonyl group, an aryl group, a carbonyl group, an ester bond, an amide bond or an ether bond, and n represents an integer of 1 to 3.
  • ⁇ 4> The curing agent according to any one of ⁇ 1> to ⁇ 3>, wherein the compound having a nitrogen functional group (A) contains a reaction product of a monofunctional and/or polyfunctional epoxy compound (C) and an amine compound (D).
  • ⁇ 8> The curing agent according to any one of ⁇ 1> to ⁇ 7>, wherein a mass ratio ((A):(B)) of the compound having a nitrogen functional group (A) to at least one compound selected from the group consisting of compounds represented by formula (1), formula (2), and formula (3) (A):(B) is 0.2:1 to 30:1.
  • ⁇ 9> The curing agent according to any one of ⁇ 1> to ⁇ 8>, which is for use in an epoxy resin.
  • a composition comprising the curing agent according to any one of ⁇ 1> to ⁇ 9> and an epoxy resin, The epoxy resin composition has a mass ratio of the curing agent to the epoxy resin (curing agent:epoxy resin) of 1:100 to 100:100.
  • the epoxy resin composition according to ⁇ 10> further comprising an inorganic filler.
  • the viscosity increase rate after being left at 110° C. for 60 minutes is 1.0 to 40.0 times,
  • R1 to R3 each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may have a nitrogen atom, an oxygen atom, a hydroxyl group, an amino group, a phenyl group, a sulfonyl group, an aryl group, a carbonyl group, an ester bond, an amide bond, or an ether bond, and n represents an integer of 2 or 3.
  • ⁇ 17> The epoxy resin composition according to ⁇ 16>, wherein the compound (D) represented by formula (11) or formula (12) contains a reaction product of a monofunctional and/or polyfunctional epoxy resin (E) and an amine compound (F).
  • R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and e is an integer of 1 to 4.
  • e is an integer of 1 to 4.
  • R 1 's each independently represent 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 represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combine to form a heterocycle having 7 or less carbon atoms
  • R 4 's each independently represent 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
  • R 5 represents a negatively charged nitrogen atom
  • R 6 represents a positively charged nitrogen atom.
  • R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and e is an integer of 1 to 4.
  • ⁇ 24> The epoxy resin composition according to any one of ⁇ 12> to ⁇ 23>, wherein the content of the inorganic filler (C) is 10% by mass or more and 90% by mass or less, based on the total mass of the epoxy resin composition.
  • ⁇ 25> The epoxy resin composition according to any one of ⁇ 12> to ⁇ 24>, wherein the epoxy resin (A) contains a p-aminophenol type epoxy resin.
  • ⁇ 27> An encapsulant comprising the cured product according to ⁇ 26>.
  • ⁇ 28> The encapsulating material according to ⁇ 27>, which is for a semiconductor.
  • ⁇ 29> An adhesive comprising the epoxy resin composition according to any one of ⁇ 10> to ⁇ 25>.
  • the first embodiment of the present invention it is possible to provide a curing agent, an epoxy resin composition, a cured product, a sealant, and an adhesive which have excellent heat resistance when made into a resin cured product, and also have excellent high-temperature stability when made into a resin composition.
  • the second embodiment of the present invention it is possible to provide an epoxy resin composition, a cured product, a sealant, and an adhesive which are excellent in reliability and injectability into a large area.
  • the curing agent of the first embodiment contains (A) a compound having a nitrogen functional group, and (B) at least one compound selected from the group consisting of compounds represented by the following formula (1), the following formula (2), and the following formula (3).
  • R 1 's each independently represent 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 represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle having 7 or less carbon atoms
  • R 4 's each independently represent 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
  • R 5 represents a negatively charged nitrogen atom
  • R 6 represents a positively charged nitrogen atom.
  • the curing agent of the first embodiment has the above-mentioned configuration, and thus has excellent durability when made into a cured resin, and also has excellent stability when made into a resin composition.
  • the resin composition using this curing agent can maintain the time during which the epoxy resin composition is low in viscosity when filling the gap between the substrate and the chip, between the package and the chip, between the interposer and the chip, etc. of the semiconductor chip.
  • the epoxy resin composition using the curing agent in the first embodiment is injected into the gap, it can sufficiently penetrate and easily fill the gap (gap) between the upper layer and the lower layer while suppressing the occurrence of voids.
  • the curing agent of the first embodiment contains (A) a compound having a nitrogen functional group (also referred to as compound (A)).
  • the compound (A) is not particularly limited, but examples thereof include aliphatic amines, alicyclic amines, aromatic amines, amide compounds, and amine adducts.
  • aliphatic amines and alicyclic amines include, but are not limited to, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane.
  • aromatic amines include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, 4-aminophenyl 4-aminobenzoate, KAYAHARD AA (manufactured by Nippon Kayaku Co., Ltd.), Ethacure 100 (manufactured by Mitsui Chemicals Fine Co., Ltd.), etc. These may be used alone or in combination of two or more.
  • amide-based compound examples include, but are not limited to, dicyandiamide and its derivatives, that is, guanidine-based compounds, or compounds in which an acid anhydride is added to an amine-based compound, and hydrazide-based compounds.
  • hydrazide compounds include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleic acid dihydrazide.
  • Guanidine compounds include, but are not limited to, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine, etc.
  • Amine adducts include compounds obtained by reacting a compound having one and/or multiple reactive groups with an amine compound (D).
  • examples of compounds having one and/or multiple reactive groups include, but are not limited to, epoxy resins, epoxy-based reactive diluents, alcohol compounds, alkyl halide compounds, isocyanate compounds, ester compounds, etc.
  • the amine adduct contains a reaction product of (C) a monofunctional and/or polyfunctional epoxy compound (also referred to as epoxy compound (C)) and (D) an amine compound (also referred to as amine compound (D)).
  • Epoxy compounds (C) include epoxy resins and epoxy-based reactive diluents, and epoxy-based reactive diluents are preferably used to reduce viscosity.
  • Epoxy resins are not particularly limited, but examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, bisphenol M type epoxy resins, bisphenol P type epoxy resins, tetrabromobisphenol A type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, tetrabromobiphenyl type epoxy resins, diphenyl ether type epoxy resins, benzophenone type epoxy resins, phenyl benzoate type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl sulfoxide type epoxy resins, diphenyl sulfone type epoxy resins, diphenyl disulfide type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, hydroquinone type epoxy resins, methylhydroquinone type epoxy resins, dibutylhydroquinone type epoxy resins, resor
  • epoxy resins modified with isocyanates or the like may also be used in combination.
  • the above-mentioned epoxy resins are not particularly limited, but for example, bisphenol F type epoxy resins can be used alone, or a combination of bisphenol F type epoxy resins and bisphenol A type epoxy resins, or a combination of bisphenol F type epoxy resins and naphthalene type epoxy resins can be used.
  • Epoxy reactive diluents include, but are not limited to, n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidy
  • the alcohol compound is not particularly limited, but examples thereof include aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, heptanol, and octanol, and ether-type alcohols having a polyethylene glycol structure, etc. These may be used alone or in combination of two or more kinds.
  • the alkyl halide compound is not particularly limited, but examples thereof include alkyl fluoride compounds, alkyl chloride compounds, alkyl bromide compounds, and alkyl iodide compounds.
  • the amount of the compound having the reactive group used in the synthesis of the amine adduct is preferably 0.01 to 1.0 equivalents, more preferably 0.05 to 0.75 equivalents, and even more preferably 0.1 to 0.5 equivalents, relative to 1 equivalent of active hydrogen of the amine compound.
  • the amine compound (D) used to obtain the amine adduct is not particularly limited, but the same compounds as the amine compounds listed above as aliphatic amines, alicyclic amines, aromatic amines, etc. can be used. Among the above compounds, it is particularly preferable that the amine compound (D) contains an aromatic amine compound. By using an aromatic amine compound, the stability and heat resistance of the epoxy resin composition can be improved.
  • the amine compound (D) when obtaining an amine adduct, preferably has an ester group or a sulfonyl group.
  • the stability of an epoxy resin composition can be improved.
  • the compound (A) may be used alone or in combination of two or more kinds.
  • the compound (A) preferably contains a secondary amine compound.
  • the stability of the epoxy resin composition is improved.
  • the compatibility of the epoxy resin when mixed with the epoxy resin is improved.
  • compound (A) preferably contains a compound represented by chemical formula (4) or (5).
  • the glass transition temperature can be improved, and a highly reliable cured resin product can be produced.
  • a cured resin product with excellent adhesive properties can be obtained.
  • R 1 to R 3 each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may have a nitrogen atom, an oxygen atom, a hydroxyl group, an amino group, a phenyl group, a sulfonyl group, an aryl group, a carbonyl group, an ester bond, an amide bond or an ether bond, and n represents an integer of 1 to 3.
  • the curing agent of the first embodiment contains at least one compound (B) (also referred to as compound B) selected from the group consisting of compounds represented by formula (1), formula (2), and formula (3).
  • R 1 's each independently represent 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 represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle having 7 or less carbon atoms
  • R 4 's each independently represent 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
  • R 5 represents a negatively charged nitrogen atom
  • R 6 represents a positively charged nitrogen atom.
  • R1 is presumed to contribute to lowering the energy of the cleavage of the N-N bond.
  • R2 and R3 are presumed to contribute to lowering the energy of the cleavage reaction by destabilizing the bond due to steric hindrance.
  • R4 is presumed to contribute to liquefying the compound and suppressing a decrease in the glass transition temperature of the resulting cured product.
  • each R 1 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.
  • the organic group is not particularly limited, and 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.
  • examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an ethylhexyl group; alkenyl groups such as a vinyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, a decynyl group, a dodecynyl group, a hexadecynyl group, and an octadecynyl group; aryl groups such as a phenyl group; and aralkyl groups including a combination of an alkyl group and a phenyl group
  • the organic group may have other substituents.
  • the substituents are not particularly limited, but examples thereof include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azido groups, thiol groups, sulfo groups, nitro groups, hydroxy groups, acyl groups, and aldehyde groups.
  • the carbon number of the organic group is 1 to 15, preferably 1 to 12, and more preferably 1 to 7. When the carbon number of 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, when the carbon number of the organic group is within the above range, the availability of raw materials is further improved.
  • R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or combine to form a heterocycle having 7 or less carbon atoms.
  • the alkyl group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include linear alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, and n-dodecyl group; branched alkyl groups such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-hexyl group, 2-octyl group, 2-decyl group, and 2-dodecyl group; and cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, and cyclododecyl group
  • the alkyl group each independently has 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 5 to 10 carbon atoms.
  • Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl group may be toxic to the human body in addition to the danger of explosion, etc.
  • By making the number of carbon atoms in the alkyl groups in R2 and R3 2 or more it is possible to avoid the use of raw materials that have the above-mentioned risks such as toxicity.
  • a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved.
  • the aryl group is not particularly limited, but examples thereof include a phenyl group and a naphthyl group.
  • the aralkyl group is not particularly limited, but examples thereof include a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.
  • R2 and R3 are preferably aralkyl groups, more preferably methylphenyl groups (benzyl groups). This tends to further improve the curing performance of the compound.
  • the number of carbon atoms in the aryl group and aralkyl group represented by R2 or R3 is not particularly limited, but is 6 to 20.
  • 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.
  • R2 and R3 may be linked to form a heterocycle having up to 7 carbon atoms.
  • the heterocycle is not particularly limited, but examples thereof include four-membered rings such as an azetidine ring; five-membered rings such as a pyrrolidine ring, a pyrrole ring, a morpholine ring, and a thiazine ring; six-membered rings such as a piperidine ring; and seven-membered rings such as a hexamethyleneimine ring and an azepine ring.
  • the heterocycle is preferably a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, or an azepine ring, more preferably a 6-membered ring or a 7-membered ring.
  • the substituent is not particularly limited, but examples thereof include an alkyl group, an aryl group, or the above-mentioned substituents in R2 and R3 . Furthermore, when the heterocycle has an alkyl group as a substituent, an example thereof is a methyl group bonded to the carbon atom adjacent to R6 .
  • R 4 each independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom.
  • the organic group is not particularly limited, and 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.
  • examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an ethylhexyl group; alkenyl groups such as a vinyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, a decynyl group, a dodecynyl group, a hexadecynyl group, and an octadecynyl group; aryl groups such as a phenyl group; and aralkyl groups including a combination of an alkyl group and a phenyl group
  • 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.
  • the organic group represented by R 4 in formula (1) or formula (2) is preferably an alkyl group, an alkenyl group, and an aralkyl group, more preferably an alkyl group and an alkenyl group, and even more preferably a branched alkyl group and a branched alkenyl group.
  • These preferred groups may have a substituent.
  • the carbon number of 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.
  • the carbon number of the organic group in R 4 is within the above range, a liquid compound having a suitable viscosity is easily obtained, and the curing performance of the compound tends to be further improved.
  • the Tg of the cured product obtained using this compound is further improved, and further, when the carbon number of the organic group in R 4 is within the above range, the availability of raw materials is further improved.
  • R 4 in formula (1) or formula (2) is 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.
  • the compound (B) preferably contains a plurality of compounds represented by the formula (1), the formula (2) or the formula (3). Note that the compound (B) may contain a plurality of compounds having different structures represented by the same formula.
  • the compound (B) contains the compounds represented by formula (1) and formula (3).
  • the content of the compound represented by formula (1) is preferably 0.1% by mass to 99.5% by mass relative to the total amount of the compounds represented by formula (1), (2), or (3), which allows easy control of the viscosity.
  • a composition containing a plurality of compounds represented by formula (1), (2), or (3) can be obtained by mixing a plurality of compounds, or by simultaneously producing a plurality of compounds in a compound production method described later.
  • the compounds represented by formula (1), formula (2) or formula (3) can be produced, for example but not limited to, by reacting an ester compound, a hydrazine compound, and a glycidyl ether compound.
  • the ester compound is not particularly limited, but examples include monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc.
  • monocarboxylate 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, and the like.
  • ethyl esters, propyl esters, etc. may be used.
  • dicarboxylate compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate, etc.
  • cyclic esters, etc. may be used.
  • cyclic esters include ⁇ -acetolactone, ⁇ -propionolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.
  • diethyl esters, dipropyl esters, etc. may be used.
  • ester compounds are preferred: 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 azelate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, gamma buty
  • 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, dini
  • dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred as the hydrazine compound.
  • dibenzylhydrazine and 1-aminopiperidine are more preferred.
  • the hydrazine compounds may be used alone or in combination of two or more kinds.
  • the glycidyl ether compound is not particularly limited, but may be, for example, a monofunctional monoglycidyl ether compound or a bifunctional or higher polyglycidyl ether compound.
  • monoglycidyl ether compounds include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, orthophenylphenol glycidyl ether, benzyl glycidyl ether, biphenylyl glycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, 3-[diethoxy(methyl)silyl]propyl glycidyl ether, etc.
  • 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.
  • polyglycidyl ether examples include aliphatic polyglycidyl ethers such as diglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol 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 of these compounds; and aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether.
  • aliphatic polyglycidyl ethers such as diglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol
  • glycidyl ether compounds are preferred: 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 dig
  • epoxy resins having an ether structure are preferred, and specific examples thereof 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 kinds.
  • 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, per 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, per mol of the primary amine of the hydrazine compound.
  • a composition containing the compounds represented by formula (2) and formula (4) can be simultaneously produced.
  • the amount of the glycidyl group of 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, per 1 mol of the primary amine of the hydrazine compound.
  • a solvent may be used in order to ensure that the reaction proceeds uniformly.
  • the solvent is not particularly limited, but examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.
  • the reaction temperature is preferably 10 to 100°C, more preferably 40 to 90°C.
  • a reaction temperature of 10°C or higher tends to speed up the reaction and improve the purity of the resulting compound.
  • a reaction temperature of 90°C or lower tends to efficiently suppress the polymerization reaction between glycidyl ether compounds, and therefore tends to improve the purity of the compound.
  • the reaction time is preferably from 1 hour to 168 hours, more preferably from 1 hour to 96 hours, and further preferably from 1 hour to 48 hours.
  • the obtained reaction product can be purified by known purification methods such as washing, extraction, recrystallization, column chromatography, etc.
  • the reaction solution dissolved in an organic solvent is washed with water, and then the organic layer is heated under normal or reduced pressure to remove unreacted raw materials and 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.
  • the organic solvent used in the above extraction is not particularly limited as long as it can dissolve the target compound, but from the standpoint of yield, purity, and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred.
  • the packing material used in column chromatography may be alumina, silica gel, or other known materials.
  • the developing solvent may be ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, or other known materials, either alone or in combination.
  • compound (B) is preferably such that n in formula (2) and formula (3) is 2 or 3. This improves the crosslink density during curing, making it possible to produce a tough cured product with improved adhesion and reliability.
  • the mass ratio of compound (A) to compound (B) is preferably 0.2:1 to 30:1, more preferably 0.5:1 to 30:1, and even more preferably 1:1 to 15:1.
  • the curing agent of the first embodiment is preferably for an epoxy resin. It can also be used as a curing accelerator.
  • the epoxy resin composition containing the curing agent of the first embodiment contains at least an epoxy resin.
  • the epoxy resin is not particularly limited, but examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone
  • bifunctional epoxy resins such as ethylene oxide-added bisphenol A type epoxy resins, ethylene oxide-added bisphenol F type epoxy resins, and propylene oxide-added bisphenol F type epoxy resins
  • trifunctional epoxy resins such as trisphenol type epoxy resins, N,N-diglycidylaminobenzene type epoxy resins, o-(N,N-diglycidylamino)toluene type epoxy resins, triazine type epoxy resins, ethylene oxide-added trisphenol type epoxy resins, and propylene oxide-added trisphenol type epoxy resins
  • tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resins, and diaminobenzene type epoxy resins
  • polyfunctional epoxy resins such as pentaerythritol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins,
  • the epoxy resin mentioned above is not particularly limited, but for example, a bisphenol F type epoxy resin can be used alone, or a combination of a bisphenol F type epoxy resin and a bisphenol A type epoxy resin, or a combination of a bisphenol F type epoxy resin and a naphthalene type epoxy resin can be used. Furthermore, an epoxy-based reactive diluent can be used in combination.
  • the epoxy-based reactive diluent mentioned above is not particularly limited, but for example, n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol
  • the epoxy resin composition of the first embodiment contains a curing agent and an epoxy resin, and the mass ratio of the curing agent to the epoxy resin (curing agent:epoxy resin) is preferably 1:100 to 100:100, more preferably 10:100 to 80:100, and particularly preferably 10:100 to 70:100.
  • the content ratio of the epoxy resin to the curing agent within the above range, high heat resistance and adhesiveness tend to be obtained.
  • the epoxy resin composition of the first embodiment may further contain other compounding agents such as a curing agent, a curing accelerator, an inorganic filler, a flame retardant, a silane coupling agent, a mold release agent, a pigment, etc., other than the compound having a nitrogen functional group (A) and the compound (B) as necessary.
  • suitable ones can be selected as appropriate.
  • the inorganic filler is not particularly limited, but examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, aluminum nitride, etc.
  • the flame retardant is not particularly limited, but examples thereof include halides, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds, etc.
  • Examples of the curing agent other than the compound (A) and the compound (B) include an acid anhydride-based curing agent, a phenol-based curing agent, and a thiol-based curing agent.
  • acid anhydride curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
  • Phenol-based hardeners include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, allyl acrylic phenol resin, etc.
  • Thiolic curing agents include, but are not limited to, thiol compounds obtained by esterification of polyols such as trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris( ⁇ -thiopropionate), pentaerythritol tetrakis( ⁇ -thiopropionate), and dipentaerythritol poly( ⁇ -thiopropionate) with thiol organic acids, alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexaneedithiol, and 1,10-decanedithiol, polyethers containing terminal thiol groups, polythioethers containing terminal thiol groups, thiol compounds obtained by reaction of epoxy compounds with hydrogen sulfide, and thiol compounds having terminal thio
  • organic filler examples include, but are not limited to, thermoplastic resins such as triblock copolymers and thermoplastic elastomers, carbon fibers, cellulose, polyethylene powder, polypropylene powder, etc. These organic fillers may be used alone or in combination of two or more. In addition to the above-mentioned components, additives such as diluents, reactive diluents, dyes, flow control agents, thickeners, strengthening agents, wetting agents, surfactants, resins, etc. may be further included.
  • 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 is obtained by curing the above-mentioned epoxy resin composition.
  • the cured product of the first embodiment is obtained by, for example, thermally curing the above-mentioned epoxy resin composition by a conventionally known method.
  • the cured product of the first embodiment can be obtained by the following method. First, the epoxy resin, the curing agent of the first embodiment, and, if necessary, an inorganic filler and/or compounding agents, etc. are thoroughly mixed until homogeneous using an extruder, kneader, roll, etc. to obtain an epoxy resin composition.
  • the epoxy resin composition is then molded using a casting machine, a transfer molding machine, a compression molding machine, an injection molding machine, etc., and further heated at about 80 to 200° C. for about 2 to 10 hours to obtain a cured product.
  • the cured product of the first embodiment can be obtained by the following method. First, the above-mentioned epoxy resin composition is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone to obtain a solution.
  • the obtained solution is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and then heated and dried to obtain a prepreg.
  • a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper
  • the obtained prepreg can be hot-press molded to obtain a cured product.
  • the epoxy resin composition of the first embodiment and the cured product obtained therefrom can be used in various applications in which epoxy resins are used as materials.
  • they are particularly useful as encapsulants (encapsulants containing the cured product of the first embodiment), encapsulants for semiconductors, adhesives (adhesives containing the epoxy resin composition of the first embodiment), printed circuit board materials, paints, composite materials, and the like.
  • encapsulants for semiconductors such as underfills and moldings
  • conductive adhesives such as anisotropic conductive films (ACFs)
  • printed wiring boards such as solder resists and coverlay films
  • composite materials such as prepregs impregnated with glass fibers or carbon fibers.
  • the cured product of the first embodiment described above can be used to make electronic components, such as, but not limited to, semiconductor sealing materials such as underfill and molding, conductive adhesives such as ACF, printed wiring boards such as solder resist and coverlay films, and composite materials such as prepregs impregnated with glass fibers or carbon fibers.
  • semiconductor sealing materials such as underfill and molding
  • conductive adhesives such as ACF
  • printed wiring boards such as solder resist and coverlay films
  • composite materials such as prepregs impregnated with glass fibers or carbon fibers.
  • the epoxy resin composition of the second embodiment is (A) an epoxy resin (also referred to as epoxy resin (A)); (B) a curing agent (also referred to as curing agent (B)) (C) an inorganic filler (also referred to as inorganic filler (C)),
  • the viscosity increase rate after being left at 110° C. for 60 minutes is 1.0 to 40.0 times,
  • the reaction rate when cured at 165°C is 80% or more and 100% or less.
  • the epoxy resin composition of the second embodiment can maintain a low viscosity state for a certain period of time or more when filled in gaps between the substrate and chip of a semiconductor chip, between the package and chip, between an interposer and a chip, etc.
  • This allows the epoxy resin composition of the second embodiment to penetrate sufficiently when injected into a gap, and the epoxy resin composition can be easily filled in the gap (space) between the upper and lower layers while suppressing the occurrence of voids.
  • it since it has sufficient adhesiveness when heated and cured, an adhesive layer with few voids and excellent adhesion between the upper and lower layers can be easily formed between the upper and lower layers, and semiconductor devices with excellent reliability can be easily manufactured with a good yield.
  • the epoxy resin composition of the second embodiment has a viscosity increase rate after being left at 110°C for 60 minutes of 1.0 to 40.0 times, preferably 1.0 to 30 times, more preferably 1.0 to 15 times, and even more preferably 1.0 to 5.0 times.
  • the composition has excellent flowability over a wide range.
  • the epoxy resin composition of the second embodiment has a reaction rate of 80% or more and 100% or less, preferably 84% or more and 100% or less, more preferably 90% or more and 100% or less, and even more preferably 95% or more and 100% or less, when cured at 165°C. By keeping the reaction rate within the above range, the composition has excellent adhesion and reliability.
  • the reaction rate can be controlled, for example, by the type of curing agent.
  • aromatic amine curing agents, amine adducts, and decomposition-type latent curing agents are examples of highly reactive curing agents. By using these, combining multiple types of other curing agents, or increasing the amount added, the reaction rate can be controlled to be higher.
  • the range of the viscosity increase rate after leaving it for 60 minutes under the condition of 110 ° C. can be controlled, for example, by selecting an appropriate type and combination of curing agent (B).
  • the viscosity increase rate tends to decrease, for example, by using an aromatic amine curing agent, and when using an amine adduct, the viscosity increase rate tends to decrease by adding an epoxy-based reactive diluent to an aromatic amine.
  • the viscosity increase rate also tends to decrease by using a decomposition type latent curing agent in combination with these.
  • the thickening rate can be controlled by using, for example, a combination of an amine compound or an amine adduct containing an aromatic ring, ester group, sulfonyl group or the like in the structure with an amine imide compound.
  • the epoxy resin composition of the second embodiment has a viscosity at 110°C of preferably 0.01 Pa ⁇ s or more and 1.0 Pa ⁇ s or less, more preferably 0.03 Pa ⁇ s or more and 0.50 Pa ⁇ s or less, and even more preferably 0.05 Pa ⁇ s or more and 0.30 Pa ⁇ s or less.
  • the viscosity is measured by the method described in the Examples section below.
  • the epoxy resin composition of the second embodiment has a maximum tan ⁇ value, measured by DMA on a cured product cured at 165°C for 2 hours, of preferably 70°C to 180°C, more preferably 80°C to 180°C, even more preferably 90°C to 180°C, and most preferably 90°C to 170°C. By keeping the temperature within the above range, the composition has excellent reliability.
  • the tan ⁇ value obtained by measuring the cured product obtained by curing the epoxy resin composition at 165°C for 2 hours with DMA can be controlled by selecting an appropriate type and combination of curing agent (B).
  • curing agent B
  • the use of aromatic amine curing agents tends to reduce the viscosity increase rate, and when an amine adduct is used, the viscosity rate tends to be 70°C or higher and 180°C or lower by adding an epoxy-based reactive diluent to an aromatic amine.
  • the use of a decomposition-type latent curing agent in combination with these also tends to keep the viscosity at 70°C or higher and 180°C or lower.
  • the epoxy resin composition of the second embodiment contains an epoxy resin.
  • the epoxy resin is not particularly limited, but examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorc
  • the epoxy resin a single bisphenol F type epoxy resin, a combination of a bisphenol F type epoxy resin and a bisphenol A type epoxy resin, a combination of a bisphenol F type epoxy resin and a naphthalene type epoxy resin, or the like can be used. From the viewpoint of achieving both permeability and reliability, it is preferable that the epoxy resin (A) contains a p-aminophenol type epoxy resin. These may be used alone or in combination of two or more. Furthermore, epoxy resins modified with isocyanate or the like can also be used in combination.
  • the epoxy resin composition of the second embodiment may further contain an epoxy-based reactive diluent.
  • the epoxy-based reactive diluent is not particularly limited, but examples thereof include n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, ethylene glycol diglycid
  • the epoxy resin content is not particularly limited, but is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 75% by mass or less, and even more preferably 15% by mass or more and 70% by mass or less, based on the total mass of the epoxy resin composition. By keeping the epoxy resin content within the above range, high adhesion tends to be obtained.
  • the epoxy resin composition of the second embodiment contains a curing agent.
  • the curing agent is not particularly limited, but examples thereof include amine-based curing agents, amide-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, catalyst-type curing agents, microcapsule-type latent curing agents, thiol-based curing agents, and decomposition-type latent curing agents.
  • Amine-based curing agents include, but are not limited to, aliphatic amines, aromatic amines, amine adducts, etc.
  • Aliphatic amines include, but are not limited to, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, etc.
  • Aromatic amines include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, KAYAHARD A-A (manufactured by Nippon Kayaku Co., Ltd.), Ethacure 100 (manufactured by Mitsui Chemicals Fine Co., Ltd.), etc.
  • the curing agent (B) may contain an amine-based curing agent.
  • the curing agent (B) contains a compound represented by the following formula (16).
  • R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
  • amine adduct a reaction product of various amines exemplified as the above-mentioned amine-based compounds with the above-mentioned epoxy resin (A), epoxy-based reactive diluent or a compound other than these compounds that is capable of reacting with an amine can be used.
  • the compound capable of reacting with an amine include an alcohol compound, an alkyl halide compound, an isocyanate compound, and an ester compound.
  • the alcohol compounds are not particularly limited, but examples include aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, pentanol, hexanol, heptanol, and octanol, and ether alcohols having a polyethylene glycol structure. These may be used alone or in combination of two or more.
  • alkyl halide compounds there is no particular limitation, but examples thereof include alkyl fluoride compounds, alkyl chloride compounds, alkyl bromide compounds, and alkyl iodide compounds. More specifically, examples include chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, alkyl chloride compounds having an ether functional group, alkyl bromide compounds, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, alkyl bromide compounds having an ether functional group, iodomethane, iodoethane, iodopropane,
  • the ester compound is not particularly limited, but examples thereof include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds.
  • 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.
  • ethyl esters, propyl esters, etc. may be used.
  • dicarboxylate ester compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate.
  • cyclic esters may be used. Specific examples of cyclic esters include ⁇ -acetolactone, ⁇ -propionolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • the curing agent (B) may contain an amine adduct.
  • the curing agent (B) contains a secondary amine compound obtained by an addition reaction of a primary amine.
  • the addition reaction is preferably a reaction in which an epoxy resin or an epoxy-based reactive diluent is added to an amine, which improves the compatibility between the epoxy resin and the curing agent and reduces voids during chip flow.
  • the viscosity increase rate at 110°C can be reduced, improving the permeability.
  • the curing agent (B) contains an amine adduct
  • the curing agent (B) contains (D) a compound represented by the following formula (11) or (12) (also referred to as compound (D)).
  • R 1 to R 3 each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may have a nitrogen atom, an oxygen atom, a hydroxyl group, an amino group, a phenyl group, a sulfonyl group, an aryl group, a carbonyl group, an ester bond, an amide bond, or an ether bond, where n is an integer of 2 or 3.
  • the glass transition temperature can be improved, making it possible to produce a highly reliable cured resin.
  • the curing agent (B) contains a reaction product of (E) a monofunctional and/or polyfunctional epoxy compound (also referred to as epoxy compound (E)) and (F) an amine compound (also referred to as amine compound (F)), and it is more preferable that the compound (D) contains a reaction product of the epoxy resin (E) and the amine compound (F). Since hydroxyl groups can be generated after the reaction of epoxy resin with amine, the adhesiveness of the cured product is improved when the synthetic compound is used as a curing agent.
  • the amine compound (F) preferably contains an aromatic amine compound. This allows the preparation of a composition with excellent stability at high temperatures and excellent flowability over a large area, and also increases the glass transition temperature of the cured product, improving adhesion and reliability.
  • the amine compound (F) contains a compound represented by the following formula (16):
  • R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
  • the amine compound (F) preferably contains an ester group or a sulfonyl group.
  • the aromatic amine compound preferably has an ester group or a sulfonyl group in the structure, which provides further high temperature stability and improves flowability over a large area.
  • the amine compound (F) preferably contains a compound represented by the following formula (16), and the viscosity after standing at 110°C for 60 minutes is preferably 0.01 Pa ⁇ s to 1.50 Pa ⁇ s.
  • the curing agent (B) preferably contains a compound represented by the following formula (13), formula (14), or formula (15). This makes it possible to prepare a composition that is stable at high temperatures and has excellent flowability over a large area.
  • 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 represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combine to form a heterocycle having 7 or less carbon atoms
  • R 4 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.
  • R 5 represents a nitrogen atom having a negative charge
  • R 6 represents a nitrogen atom having a positive charge.
  • n in the formula (14) and the formula (15) is preferably 2 or 3. This improves the crosslink density during curing, making it possible to produce a tough cured product, and improving adhesion and reliability.
  • the amount of epoxy compound used in the synthesis of the amine adduct is preferably 0.1 to 1.0 equivalent, more preferably 0.1 to 0.75 equivalent, and even more preferably 0.1 to 0.5 equivalent, per equivalent of active hydrogen of the amine compound.
  • Amide-based hardeners include, but are not limited to, dicyandiamide and its derivatives, such as guanidine-based compounds, compounds in which acid anhydrides are added to amine-based compounds, and hydrazide-based compounds.
  • Hydrazide compounds include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, maleic acid dihydrazide, etc.
  • Guanidine compounds include, but are not limited to, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine, etc.
  • Phenol-based hardeners include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, allyl acrylic phenol resin, etc.
  • acid anhydride curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.
  • the active ester compound constituting the active ester-based curing agent the active ester compound disclosed in JP-A-2004-277460 may be used, or a commercially available product may also be used.
  • Commercially available active ester compounds are not limited to the following, but are preferably, for example, those containing a dicyclopentadienyldiphenol structure, acetylated phenol novolac, and benzoylated phenol novolac, and more preferably those containing a dicyclopentadienyldiphenol structure.
  • Examples of compounds containing a dicyclopentadienyldiphenol structure include, but are not limited to, EXB9451, EXB9460, EXB9460S, and HPC-8000-65T (manufactured by DIC Corporation), an acetylated product of phenol novolac such as DC808 (manufactured by Japan Epoxy Resins Co., Ltd.), and a benzoylated product of phenol novolac such as YLH1026 (manufactured by Japan Epoxy Resins Co., Ltd.).
  • Catalytic curing agents include, but are not limited to, cationic thermosetting catalysts, BF3-amine complexes, etc.
  • Microcapsule-type latent hardeners include, but are not limited to, Novacure HX-3721, HX-3722, HX-3613, HX-3921HP, HXA9322HP, and HXA-9382HP (manufactured by Asahi Kasei Corporation).
  • Thiolic curing agents include, but are not limited to, thiol compounds obtained by esterification of polyols such as trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris( ⁇ -thiopropionate), pentaerythritol tetrakis( ⁇ -thiopropionate), and dipentaerythritol poly( ⁇ -thiopropionate) with thiol organic acids, alkyl polythiol compounds such as 1,4-butanedithiol, 1,6-hexaneedithiol, and 1,10-decanedithiol, polyethers containing terminal thiol groups, polythioethers containing terminal thiol groups, thiol compounds obtained by reaction of epoxy compounds with hydrogen sulfide, and thiol compounds having terminal thio
  • decomposition-type latent hardeners include, but are not limited to, compounds obtained by reacting ester compounds, hydrazine compounds, and glycidyl ether compounds.
  • the ester compound is not particularly limited, but examples thereof include monocarboxylic acid ester compounds and dicarboxylic acid ester compounds.
  • monocarboxylate 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.
  • dicarboxylate compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, etc.
  • cyclic esters, etc. may be used.
  • cyclic esters include ⁇ -acetolactone, ⁇ -propionolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.
  • diethyl esters, dipropyl esters, etc. may be used.
  • ester compounds are preferred: 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 azelate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, gamma buty
  • dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred as hydrazine compounds.
  • dibenzylhydrazine and 1-aminopiperidine are more preferred from the viewpoints of availability and safety.
  • the hydrazine compounds may be used alone or in combination of two or more kinds.
  • the glycidyl ether compound is not particularly limited, but for example, a monofunctional monoglycidyl ether compound or a difunctional or higher functional polyglycidyl ether compound can be used.
  • 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-butylpheny
  • 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, glycerin polyglycidyl ether, and the like.
  • 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.
  • glycidyl ether compounds are preferred: 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 dig
  • epoxy resins having an ether structure are preferred, specific examples of which 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 kinds.
  • 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, per 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, per mol of the primary amine of the hydrazine compound.
  • the amount of the glycidyl group of the glycidyl ether compound added relative to 1 mole of the primary amine of the hydrazine compound is preferably 0.1 mole to 3.0 moles, more preferably 0.3 mole to 2.0 moles, and even more preferably 0.5 mole to 1.0 mole.
  • a solvent may be used to ensure that the reaction proceeds uniformly.
  • the solvent is not particularly limited, but examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.
  • the reaction temperature is preferably 10 to 100°C, more preferably 40 to 90°C.
  • the reaction temperature is 10°C or higher, the reaction proceeds faster and the purity of the resulting compound tends to be improved.
  • the reaction temperature is 90°C or lower, the polymerization reaction between glycidyl ether compounds can be efficiently suppressed, so the purity of the compound tends to be improved.
  • the reaction time is preferably from 1 hour to 168 hours, more preferably from 1 hour to 96 hours, and even more preferably from 1 hour to 48 hours.
  • the resulting reaction product can be purified by known purification methods such as washing, extraction, recrystallization, column chromatography, etc.
  • the reaction solution dissolved in an organic solvent can be washed with water, and then the organic layer can be heated under normal or reduced pressure to remove unreacted raw materials and organic solvent from the reaction solution and recover the target compound.
  • the target compound can 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 raw material residues, but 1-hexane, 1-pentane, and cyclohexane are preferred from the standpoints of yield, purity, and ease of removal.
  • the organic solvent used in the above extraction is not particularly limited as long as it can dissolve the target compound, but from the standpoint of yield, purity, and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred.
  • the packing material used in column chromatography may be alumina, silica gel, or other known materials
  • the developing solvent may be ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, or other known materials, either alone or in combination.
  • the content of the curing agent is not particularly limited, but is preferably 0.5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less, based on the total mass of the epoxy resin composition.
  • the epoxy resin composition of the second embodiment it is preferable to use two types of curing agents in combination from the viewpoint of achieving both stability and reactivity.
  • two types in combination it is preferable to use a combination of an amine-based curing agent and a decomposition-type latent curing agent.
  • the amine-based curing agent is an amine adduct from the viewpoint of stability.
  • the content of the amine-based curing agent is preferably 0.5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and further preferably 10% by mass or more and 25% by mass or less, based on the total mass of the epoxy resin composition.
  • the content of the decomposable latent curing agent is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, and even more preferably 0.1% by mass or more and 10% by mass or less, based on the total mass of the epoxy resin composition.
  • two or more types of curing agents may be used.
  • the mass ratio of the amine-based hardener is preferably in the range of 0.2 to 30 relative to 1 mass of the decomposable latent hardener, more preferably 0.5 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
  • the amount of hardener within the above range, particularly the mass ratio of the amine-based hardener to 1 mass of the decomposable latent hardener, between 1 and 20, a hardened product with high heat resistance tends to be obtained.
  • the epoxy resin composition of the second embodiment contains an inorganic filler.
  • the inorganic filler is not particularly limited, but examples thereof include fused silica, crystalline silica, alumina, talc, silicon nitride, and aluminum nitride.
  • the content of the inorganic filler is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 75% by mass or less, based on the total mass of the epoxy resin composition.
  • the epoxy resin composition of the second embodiment may further contain other compounding agents such as a curing accelerator, a flame retardant, a silane coupling agent, a release agent, a pigment, etc., as necessary.
  • suitable ones can be selected as appropriate.
  • the flame retardant is not particularly limited, but examples thereof include halides, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds, etc.
  • the cured product of the second embodiment is a cured product of the epoxy resin composition of the second embodiment.
  • the cured product of the second embodiment is obtained by curing the above-mentioned epoxy resin composition.
  • the cured product of the second embodiment is obtained by, for example, thermally curing the above-mentioned epoxy resin composition by a conventionally known method.
  • the cured product of the second embodiment can be obtained by the following method.
  • the above-mentioned (A) epoxy resin, (B) curing agent, (C) inorganic filler, and/or compounding agents are thoroughly mixed using an extruder, kneader, roll, etc. until homogeneous to obtain an epoxy resin composition.
  • the epoxy resin composition is then molded using a casting machine, transfer molding machine, compression molding machine, injection molding machine, etc., and further heated at about 80 to 200°C for about 2 to 10 hours to obtain a cured product.
  • the cured product of the second embodiment can be obtained by the following method.
  • a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone to obtain a solution.
  • the obtained solution is impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg.
  • the obtained prepreg can be hot-press molded to obtain a cured product.
  • the cured product of the second embodiment can be used to produce an electronic component.
  • Specific examples of the electronic component are the same as those of the electronic component using the cured product of the second embodiment.
  • the first embodiment will be described in more detail with reference to Synthesis Examples, Examples, and Comparative Examples, but the first embodiment is not limited thereto.
  • “parts” and “%” are by mass unless otherwise specified.
  • the curing agent of the first embodiment was synthesized.
  • the synthesized product was measured by ESI-MS, IR, NMR, etc., to confirm that the target compound was synthesized.
  • thermosetting resin composition used as a thermosetting adhesive was prepared according to the examples described below. The properties of the obtained epoxy resin composition were measured.
  • Viscosity increase rate viscosity after storage B ⁇ initial viscosity A The measurement time was measured from the point when the epoxy resin composition was dropped onto the hot plate that had reached the flow temperature and the measurement was started 10 seconds after the epoxy resin composition was sandwiched between the measurement plates. The lower the viscosity increase ratio, the better the stability at high temperatures.
  • the viscosity increase ratio is preferably 20 or less, and more preferably 15 or less.
  • the glass transition temperature (Tg) (°C) of the cured product of the thermosetting epoxy resin composition was determined by measuring the storage modulus (MPa) and loss modulus (MPa) of a test piece of 20 mm length ⁇ 10 mm width ⁇ 2 mm thickness at a temperature rise of 5°C/min using a dynamic viscoelasticity measuring device RSA-G2 (manufactured by TA Instruments), and determining the temperature at which tan ⁇ was maximum.
  • the glass transition temperature is preferably 73°C or higher, more preferably 75°C or higher.
  • Shear Adhesive Strength Measurement Test pieces were prepared in accordance with JIS K6850 using the epoxy resin compositions of the examples and comparative examples described below.
  • adherend a 25 mm wide x 50 mm long x 0.5 mm thick adherend (cold-rolled copper plate) conforming to JIS C3141 was used.
  • An uncured test piece was placed in a small high-temperature chamber "ST-110B2" manufactured by ESPEC Corporation, which had a stable internal temperature of 165°C, and heated for 2 hours to obtain a shear adhesive strength measurement test piece. After 2 hours, the structure (shear adhesive strength measurement test piece) was removed from the small high-temperature chamber, left in a room temperature environment, and cooled to room temperature.
  • the maximum load at which the adhesive surface of the test piece breaks and the test piece separates was measured using a load cell of 5 kN and a speed of 5 mm/min using Shimadzu Corporation's "AGX-5kNX,” and the value obtained by dividing the maximum load by the adhesive area was taken as the shear adhesive strength.
  • Epoxy resin Epoxy resin A'("jER828" manufactured by Mitsubishi Chemical Corporation
  • the hardener of the second embodiment was synthesized.
  • the synthesized product was measured by ESI-MS, IR, NMR, etc., and it was confirmed that the desired compound had been synthesized.
  • thermosetting resin composition to be used as a thermosetting adhesive was prepared according to the examples described below.
  • the various properties of the obtained epoxy resin composition were measured as described below.
  • Viscosity increase rate was measured by the method described in (2) Viscosity increase rate measurement in the examples of the first embodiment.
  • Shear Adhesive Strength Measurement The shear adhesive strength was measured by the method described in (4) Shear adhesive strength measurement in the examples of the first embodiment.
  • the structure (shear bond strength measurement test piece) was removed from the small high-temperature chamber and left in a room temperature environment and cooled to room temperature.
  • the sample was left in an environment of 30°C and 60% RH for 192 hours, and then left at 260°C for 30 seconds. It was left in a room temperature environment and cooled to room temperature.
  • the maximum load at which the adhesive surface of the test piece breaks and the test piece separates is measured using a Shimadzu Corporation "AGX-5kNX" at a load cell of 5 kN and a speed of 5 mm/min, and the maximum load at which the test piece separates is divided by the adhesive area to determine the shear adhesive strength after the reliability test.
  • the higher the shear adhesive strength value after the reliability test the better the reliability. If the shear adhesive strength value after the reliability test is 60 or more, it can be said that the reliability is excellent.
  • An epoxy resin composition was prepared by kneading 5 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 15 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation), 7 g of epoxy resin F (“CDMDG” manufactured by Resonac Inc.), 2 g of epoxy resin G ("YED-216D” manufactured by Mitsubishi Chemical Corporation), 55 g of inorganic filler B ("SE203G-SEJ” manufactured by Admatechs Co., Ltd.), and 0.1 g of additive B ("MA100" manufactured by Mitsubishi Chemical Corporation) using a three-roll mill (BR-150HCV manufactured by AIMEX Corporation), adding 15 g of curing agent A and 0.9 g of curing agent L, and kneading again using the three-roll mill (BR-150HCV manufactured by AIMEX Corporation).
  • the “thickening rate” was evaluated by the above-mentioned thickening rate measurement method (1), the “reaction rate” was evaluated by the reaction rate measurement method (2), the “glass transition temperature” was evaluated by the glass transition temperature measurement method (3), the “penetration” was evaluated by the penetration measurement method (4), the "dispersibility” was evaluated by the blended product appearance evaluation method (5), the “adhesion” was evaluated by the shear bond strength measurement method (6), the "reliability” was evaluated by the shear bond strength measurement method after reliability test (7), and the "thermal expansion” was evaluated by the thermal expansion measurement method (8).
  • Example 2 An epoxy resin composition was prepared in the same manner as in Example 1 except that 7 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 15 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation), and 7 g of epoxy resin F (“CDMDG” manufactured by Resonac Corporation) were used as the epoxy resins, and 15 g of curing agent A and 0.9 g of curing agent I were used as the curing agents, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • EXA-830CRP manufactured by DIC Corporation
  • 15 g of epoxy resin B (“jER630LSD” manufactured by Mitsubishi Chemical Corporation)
  • CDMDG epoxy resin F
  • Example 3 An epoxy resin composition was prepared in the same manner as in Example 1, except that 15 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 15 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, and 15 g of curing agent E and 0.9 g of curing agent I were used as the curing agents, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • 15 g of epoxy resin A (“EXA-830CRP” manufactured by DIC Corporation)
  • 15 jER630LSD” manufactured by Mitsubishi Chemical Corporation) 15 g of curing agent E and 0.9 g of curing agent I were used as the curing agents, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 4 An epoxy resin composition was prepared in the same manner as in Example 3, except that the curing agents were changed to 15 g of Curing agent A and 0.9 g of Curing agent I, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • Example 5 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of Curing agent A and 0.9 g of Curing agent J, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • Example 6 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of curing agent A and 0.9 g of curing agent K, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • Example 7 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of curing agent A and 0.9 g of curing agent L, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • Example 8 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of Curing agent A and 0.9 g of Curing agent M, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion properties were evaluated.
  • Example 9 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of curing agent F and 0.9 g of curing agent I, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion properties were evaluated.
  • Example 10 An epoxy resin composition was prepared in the same manner as in Example 1, except that 22 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 22 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, 24 g of curing agent A and 1.4 g of curing agent L were used as the curing agents, and 30 g of inorganic filler B ("SE203G-SEJ” manufactured by Admatechs Co., Ltd.) were used, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • 22 g of epoxy resin A (“EXA-830CRP” manufactured by DIC Corporation) and 22 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin
  • 24 g of curing agent A and 1.4 g of curing agent L were used as the curing agents
  • Example 11 An epoxy resin composition was prepared in the same manner as in Example 1, except that 5 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 10 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation), and 5 g of epoxy resin F (“CDMDG” manufactured by Resonac Corporation) were used as the epoxy resin, 10 g of curing agent A and 0.6 g of curing agent L were used as the curing agents, and 70 g of inorganic filler B (“SE203G-SEJ” manufactured by Admatechs Corporation) were used, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • EXA-830CRP manufactured by DIC Corporation
  • 10 g of epoxy resin B (“jER630LSD” manufactured by Mitsubishi Chemical Corporation)
  • CDMDG epoxy resin F
  • 10 g of curing agent A and 0.6 g of curing agent L were used as the curing agents
  • Example 12 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of Curing agent D and 0.9 g of Curing agent I, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • Example 13 An epoxy resin composition was prepared in the same manner as in Example 1 except that 8 g of epoxy resin A (manufactured by DIC Corporation, "EXA-830CRP"), 15 g of epoxy resin B (manufactured by Mitsubishi Chemical Corporation, "jER630LSD”), 2 g of epoxy resin C (manufactured by DIC Corporation, "HP4032D”), 1 g of epoxy resin D (manufactured by Mitsubishi Chemical Corporation, "YX-4000H”), 3 g of epoxy resin F (manufactured by Resonac Corporation, "CDMDG”), and 1 g of epoxy resin G (manufactured by Mitsubishi Chemical Corporation, "YED-216D”) were used as the epoxy resins, and 15 g of curing agent B and 1.4 g of curing agent L were used as the curing agents, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 14 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agent was changed to 15 g of Curing Agent D and 0.9 g of Curing Agent I, and 0.3 g of Additive A ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) was used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • Additive A (“KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 15 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agent was changed to 0.9 g of curing agent L and 15 g of diaminodiphenyl sulfone, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion property were evaluated.
  • Example 16 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of Curing Agent G and 0.9 g of Curing Agent L, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion properties were evaluated.
  • Example 17 An epoxy resin composition was prepared in the same manner as in Example 1 except that 9 g of epoxy resin A (manufactured by DIC Corporation, "EXA-830CRP"), 16 g of epoxy resin B (manufactured by Mitsubishi Chemical Corporation, "jER630LSD”), 2 g of epoxy resin C (manufactured by DIC Corporation, "HP4032D”), 1 g of epoxy resin D (manufactured by Mitsubishi Chemical Corporation, "YX-4000H”), 3 g of epoxy resin F (manufactured by Resonac Corporation, "CDMDG”), and 1 g of epoxy resin G (manufactured by Mitsubishi Chemical Corporation, "YED-216D”) were used as the epoxy resins, 17 g of curing agent B and 1.6 g of curing agent I were used as the curing agents, and 50 g of inorganic filler A (manufactured by Admatechs Corporation, "SE2200-SEJ”) were used, and the viscosity increase
  • Example 18 An epoxy resin composition was prepared in the same manner as in Example 1 except that 12 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 12 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, 7 g of diethyldiaminodiphenylmethane and 4 g of diethyltoluenediamine were used as the curing agent, 65 g of inorganic filler A (“SE2200-SEJ” manufactured by Admatechs Co., Ltd.) were used, and 0.3 g of additive A (“KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) were used, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • 12 g of epoxy resin A (“EXA-830CRP” manufactured by DIC Corporation) and 12 g of epoxy resin B ("jER630LSD”
  • Example 19 An epoxy resin composition was prepared in the same manner as in Example 1, except that 17 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 17 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, and 10 g of curing agent B and 0.5 g of curing agent L were used as the curing agents, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • 17 g of epoxy resin A (“EXA-830CRP” manufactured by DIC Corporation)
  • 17 g of epoxy resin B (“jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin
  • 10 g of curing agent B and 0.5 g of curing agent L were used as the curing agents, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 20 An epoxy resin composition was prepared in the same manner as in Example 1, except that 15 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 15 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, and 5 g of curing agent B and 10.4 g of curing agent L were used as the curing agents, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • 15 g of epoxy resin A (“EXA-830CRP” manufactured by DIC Corporation)
  • 15 g of epoxy resin B (“jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin
  • 5 g of curing agent B and 10.4 g of curing agent L were used as the curing agents, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 21 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agents were changed to 15 g of Curing Agent A and 0.9 g of Curing Agent M, and no inorganic filler was used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion properties were evaluated.
  • Example 22 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agent was changed to 15 g of Curing agent A and 0.9 g of Curing agent M, and 10 g of Inorganic filler B ("SE203G-SEJ" manufactured by Admatechs Co., Ltd.) was used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • SE203G-SEJ manufactured by Admatechs Co., Ltd.
  • Example 23 An epoxy resin composition was prepared in the same manner as in Example 1, except that 7 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 22 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, and 15 g of curing agent G and 0.9 g of curing agent L were used as the curing agents, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • 7 g of epoxy resin A (“EXA-830CRP” manufactured by DIC Corporation)
  • 22 g of epoxy resin B (“jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin
  • 15 g of curing agent G and 0.9 g of curing agent L were used as the curing agents, and the viscosity increase rate, reactivity, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 24 An epoxy resin composition was prepared in the same manner as in Example 1, except that 15 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 15 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, and 15 g of curing agent A was used as the curing agent, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • 15 g of epoxy resin A (“EXA-830CRP” manufactured by DIC Corporation) and 15 g of epoxy resin B (“jER630LSD” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin
  • 15 g of curing agent A was used as the curing agent, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 25 An epoxy resin composition was prepared in the same manner as in Example 1, except that 20 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation), 7 g of epoxy resin C ("HP4032D” manufactured by DIC Corporation), and 7 g of epoxy resin D ("YX-4000H” manufactured by Mitsubishi Chemical Corporation) were used as the epoxy resin, 16 g of curing agent C and 1.0 g of curing agent L were used as the curing agent, and 50 g of inorganic filler A (“SE2200-SEJ” manufactured by Admatechs Co., Ltd.) were used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 26 An epoxy resin composition was prepared in the same manner as in Example 1, except that 17 g of epoxy resin B (manufactured by Mitsubishi Chemical Corporation, "jER630LSD”), 9 g of epoxy resin E (manufactured by Resonac Corporation, "PETG”), and 2 g of epoxy resin F (manufactured by Resonac Corporation, "CDMDG”) were used as the epoxy resin, 17 g of curing agent A and 0.8 g of curing agent L were used as the curing agents, and 55 g of inorganic filler B (manufactured by Admatechs Corporation, "SE203G-SEJ”) were used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 27 An epoxy resin composition was prepared in the same manner as in Example 1, except that 21 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation), 5 g of epoxy resin C ("HP4032D” manufactured by DIC Corporation), and 2 g of epoxy resin F (“CDMDG” manufactured by Resonac Corporation) were used as the epoxy resin, 17 g of curing agent A and 0.8 g of curing agent L were used as the curing agents, and 55 g of inorganic filler B (“SE203G-SEJ” manufactured by Admatechs Corporation) were used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Example 28 An epoxy resin composition was prepared in the same manner as in Example 4, except that the curing agent was changed to 15 g of curing agent A and 0.9 g of curing agent L, and 65 g of inorganic filler B ("SE203G-SEJ" manufactured by Admatechs Co., Ltd.) was used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion property were evaluated.
  • SE203G-SEJ inorganic filler B
  • Example 29 An epoxy resin composition was prepared in the same manner as in Example 1, except that the epoxy resin was changed to 31 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation), the curing agent was changed to 12 g of curing agent H and 2 g of curing agent L, and 55 g of inorganic filler B (“SE203G-SEJ” manufactured by Admatechs Corporation) was used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • epoxy resin B jER630LSD
  • SE203G-SEJ inorganic filler B
  • Example 30 An epoxy resin composition was prepared in the same manner as in Example 1, except that the epoxy resin was changed to 34 g of epoxy resin B ("jER630LSD” manufactured by Mitsubishi Chemical Corporation), the curing agent was changed to 10 g of Ethacure 100 Plus (a curing agent containing diethyltoluenediamine, manufactured by Mitsui Fine Chemicals) and 1 g of curing agent L, and 55 g of inorganic filler B (“SE203G-SEJ” manufactured by Admatechs Corporation) was used, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesion, reliability, and linear thermal expansion properties were evaluated.
  • Ethacure 100 Plus a curing agent containing diethyltoluenediamine, manufactured by Mitsui Fine Chemicals
  • SE203G-SEJ inorganic filler B
  • Example 31 An epoxy resin composition was prepared in the same manner as in Example 19, except that the curing agents were changed to 15 g of curing agent B and 0.75 g of curing agent L, and the viscosity increase rate, reaction rate, glass transition temperature, permeability, dispersibility, adhesiveness, reliability, and linear thermal expansion properties were evaluated.
  • the first embodiment of the present invention also includes the following embodiments.
  • a curing agent comprising: (A) a compound having a nitrogen functional group; and (B) at least one compound selected from the group consisting of compounds represented by the following formula (1), (2), and (3):
  • R 1 's each independently represent 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 represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle having 7 or less carbon atoms
  • R 4 's each independently represent 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
  • R 5 represents a negatively charged nitrogen atom
  • R 6 represents a positively charged nitrogen atom.
  • R 1 to R 3 each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may have a nitrogen atom, an oxygen atom, a hydroxyl group, an amino group, a phenyl group, a sulfonyl group, an aryl group, a carbonyl group, an ester bond, an amide bond or an ether bond, and n represents an integer of 1 to 3.
  • ⁇ 4> The curing agent according to any one of ⁇ 1> to ⁇ 3>, wherein the compound having a nitrogen functional group (A) contains a reaction product of a monofunctional and/or polyfunctional epoxy compound (C) and an amine compound (D).
  • ⁇ 8> The curing agent according to any one of ⁇ 1> to ⁇ 7>, wherein a mass ratio ((A):(B)) of the compound having a nitrogen functional group (A) to at least one compound selected from the group consisting of compounds represented by formula (1), formula (2), and formula (3) (A):(B) is 0.2:1 to 30:1.
  • ⁇ 9> The curing agent according to any one of ⁇ 1> to ⁇ 8>, which is for use in an epoxy resin.
  • An epoxy resin composition comprising the curing agent according to any one of ⁇ 1> to ⁇ 9> and an epoxy resin, wherein a mass ratio of the curing agent to the epoxy resin (curing agent:epoxy resin) is 1:100 to 100:100.
  • ⁇ 11> A cured product of the epoxy resin composition according to ⁇ 10>.
  • ⁇ 12> An encapsulant comprising the cured product according to ⁇ 11>.
  • ⁇ 13> The encapsulating material according to ⁇ 12>, which is for a semiconductor.
  • An adhesive comprising the epoxy resin composition according to ⁇ 10>.
  • the second embodiment of the present invention also includes the following embodiment.
  • the viscosity increase rate after standing for 60 minutes under a condition of 110°C is 1.0 times or more and 40.0 times or less,
  • R 1 to R 3 each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may have a nitrogen atom, an oxygen atom, a hydroxyl group, an amino group, a phenyl group, a sulfonyl group, an aryl group, a carbonyl group, an ester bond, an amide bond, or an ether bond, and n represents an integer of 2 or 3.
  • ⁇ 5> The epoxy resin composition according to ⁇ 4>, wherein the compound (D) represented by formula (11) or formula (22) contains a reaction product of a monofunctional and/or polyfunctional epoxy resin (E) and an amine compound (F).
  • R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and e is an integer of 1 to 4.
  • (B) curing agent contains a compound represented by the following formula (13), formula (14), or formula (15):
  • R 1 's each independently represent 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 represent an unsubstituted or substituted alkyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms, or combine to form a heterocycle having 7 or less carbon atoms
  • R 4 's each independently represent 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
  • R 5 represents a negatively charged nitrogen atom
  • R 6 represents a positively charged nitrogen atom.
  • R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen, and e is an integer of 1 to 4.
  • ⁇ 12> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 11>, wherein the content of the inorganic filler (C) is 10 mass% or more and 90 mass% or less, based on the total mass of the epoxy resin composition.
  • ⁇ 13> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 12>, wherein the epoxy resin (A) contains a p-aminophenol type epoxy resin.
  • ⁇ 15> An encapsulant comprising the cured product according to ⁇ 14>.
  • ⁇ 16> The encapsulating material according to ⁇ 15>, which is for a semiconductor.
  • ⁇ 17> An adhesive comprising the epoxy resin composition according to any one of ⁇ 1> to ⁇ 13>.
  • the epoxy resin composition of this embodiment has industrial applicability as a sealant, adhesive, printed circuit board material, paint, composite material, semiconductor sealant such as underfill and molding, conductive adhesive such as ACF, printed wiring board such as solder resist and coverlay film, composite material such as prepreg impregnated with glass fiber or carbon fiber, etc.

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