WO2023127800A1 - エポキシ樹脂組成物、硬化物、封止材及び接着剤 - Google Patents

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
WO2023127800A1
WO2023127800A1 PCT/JP2022/047933 JP2022047933W WO2023127800A1 WO 2023127800 A1 WO2023127800 A1 WO 2023127800A1 JP 2022047933 W JP2022047933 W JP 2022047933W WO 2023127800 A1 WO2023127800 A1 WO 2023127800A1
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Prior art keywords
epoxy resin
resin composition
compound
group
curing agent
Prior art date
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PCT/JP2022/047933
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English (en)
French (fr)
Japanese (ja)
Inventor
凌輔 岡本
直弥 上村
賢三 鬼塚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Application filed by Asahi Kasei Corp, Asahi Chemical Industry Co Ltd filed Critical Asahi Kasei Corp
Priority to CN202280074584.XA priority Critical patent/CN118302470A/zh
Priority to KR1020247009291A priority patent/KR20240044519A/ko
Priority to US18/713,564 priority patent/US20250034319A1/en
Priority to JP2023571011A priority patent/JPWO2023127800A1/ja
Publication of WO2023127800A1 publication Critical patent/WO2023127800A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4035—Hydrazines; Hydrazides
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4042—Imines; Imides
    • 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
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
    • 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
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/686—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 catalysts used containing nitrogen
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1535—Five-membered rings
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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
    • 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
    • C08G2170/00—Compositions for adhesives

Definitions

  • the present invention relates to epoxy resin compositions, cured products, sealing materials and adhesives.
  • Epoxy resins are used in coatings, electrical and electronic insulating materials, adhesives, etc., because the cured products thereof have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc. used for a wide range of purposes.
  • Patent Document 1 discloses a resin used for a semiconductor package.
  • Epoxy resin compositions generally used at present are so-called two-component epoxy resin compositions in which an epoxy resin and a curing agent are mixed at the time of use.
  • a two-component epoxy resin composition can be cured at room temperature, but the epoxy resin and curing agent must be stored separately and, if necessary, weighed and mixed before use. is complicated. In addition, since the usable time is limited, a large amount cannot be mixed in advance, and the frequency of blending increases, which inevitably leads to a decrease in efficiency.
  • Patent Document 2 discloses an epoxy resin composition using liquid aromatic amines.
  • the latent curing agent that constitutes the one-component epoxy resin composition is required to have both good curability and storage stability after being mixed with the epoxy resin. There is also a demand for good permeability and adhesiveness in narrow gaps and between dense fibers such as carbon fibers and glass fibers.
  • Patent Document 1 discloses a resin composition using an aromatic amine compound as a curing agent, but the curing agent used is solid, and it is considered difficult to penetrate narrow gaps. have a point.
  • Patent Document 2 discloses an epoxy resin composition using a liquid aromatic amine compound as a curing agent. However, it has the problem that it is complicated to handle.
  • an object of the present invention is to provide an epoxy resin composition having good adhesiveness, a cured product of the epoxy resin composition, a sealing material, and an adhesive.
  • the inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, an epoxy resin composition containing a specific curing agent and having a molecular weight of the curing agent and the number of heteroatoms in the structure within a specific range has been developed as described above.
  • the present inventors have found that the problem can be solved and completed the present invention. That is, the present invention is as follows.
  • Epoxy resin composition [2] The epoxy resin composition according to [1] above, wherein the (B) curing agent having a heteroatom contains an amine imide compound represented by the following formula (1), formula (2), or formula (3).
  • each R 1 is independently a hydrogen atom, or a C 1 to 15 group optionally having a hydroxyl group, a carbonyl group, an ester bond, or an ether bond
  • R 2 and R 3 are each independently an unsubstituted or substituted alkyl group, aryl group, aralkyl group having 1 to 12 carbon atoms, or R 2 and R 3 represent a heterocyclic ring having 7 or less carbon atoms linked
  • n represents an integer of 1 to 3.
  • R 5 and R 6 each independently have a hydrogen atom, or a hydroxyl group, a carbonyl group, an ester bond, or an ether bond, and having 1 to 15 carbon atoms, represents a monovalent or n-valent organic group, and n represents an integer of 2 to 3.
  • R 7 represents a monovalent or 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, and n is represents an integer from 2 to 3.
  • the content of the (D) stabilizer is, relative to 100 parts by mass of the (A) epoxy resin, The epoxy resin composition according to [6] or [7], which is 1 part by mass or more and 30 parts by mass or less.
  • a sealing material comprising the cured product according to [9] above.
  • the sealing material according to the above [10] which is a semiconductor sealing material.
  • An adhesive comprising the epoxy resin composition according to any one of [1] to [8].
  • an epoxy resin composition having good adhesiveness, a cured product of the epoxy resin composition, a sealing material, and an adhesive.
  • this embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents, and the present invention can be implemented in various modifications within the scope of the gist thereof. .
  • the epoxy resin composition of this embodiment is (A) an epoxy resin; (B) a curing agent having a heteroatom (hereinafter sometimes referred to as (B) a curing agent), and the molecular weight ⁇ of the (B) curing agent having a heteroatom (hereinafter simply may be referred to as "molecular weight ⁇ ") is 200 ⁇ ⁇ ⁇ 1200, and the molecular weight ⁇ and the heteroatom number ⁇ in the structure of the curing agent (B) having a heteroatom (hereinafter simply referred to as the "heteroatom number ⁇ ′′) is 30 ⁇ / ⁇ 95.
  • the epoxy resin composition of the present embodiment has excellent adhesiveness due to the above configuration.
  • This factor is considered as follows, but the factor is not limited to these. That is, when the molecular weight ⁇ of the (B) curing agent having a heteroatom is 200 or more, the crosslink length during curing becomes long and a tough structure is obtained, so cohesive failure of the cured product can be suppressed and adhesion is improved. expected to improve. On the other hand, when the molecular weight ⁇ of the (B) curing agent having a heteroatom is 1200 or less, the (B) curing agent has excellent dispersibility and is sufficiently dispersed in the (A) epoxy resin. It is thought that sufficient adhesive strength can be obtained as a result of the ability to exhibit excellent curability.
  • the value of the ratio ⁇ / ⁇ consisting of the molecular weight ⁇ and the heteroatom number ⁇ in the structure of the (B) curing agent is 95 or less, so that the (B) curing agent having a heteroatom has a polarity It is thought that the number of functional groups is increased, and the epoxy resin composition of the present embodiment and the adherend are strongly adhered by intermolecular bonding.
  • the ratio ⁇ / ⁇ between the molecular weight ⁇ and the heteroatom number ⁇ in the structure of the (B) curing agent having a heteroatom is 30 or more, the (B) curing agent and the (A) epoxy It is believed that the compatibility with the resin increases and the epoxy resin composition can be sufficiently cured, resulting in sufficient adhesive strength.
  • the lower limit of the molecular weight ⁇ of the (B) heteroatom-containing curing agent is 200 or more, preferably 220 or more, and more preferably 250 or more.
  • the upper limit of the molecular weight ⁇ of the (B) heteroatom-containing curing agent is 1,200 or less, preferably 1,100 or less, more preferably 1,000 or less, and even more preferably 900.
  • the molecular weight ⁇ of the (B) heteroatom-containing curing agent can be measured by a mass spectrometer (ESI-MS).
  • the lower limit of the ratio ⁇ / ⁇ between the molecular weight ⁇ and the heteroatom number ⁇ in the structure of the (B) curing agent having a heteroatom is 30 or more. , is preferably 35 or more, more preferably 40 or more.
  • the upper limit of the ratio ⁇ / ⁇ is 95 or less, preferably 90 or less, and more preferably 80 or less.
  • the heteroatom number ⁇ in the structure of the (B) curing agent having a heteroatom can be measured using a mass spectrometer (ESI-MS).
  • the heteroatom number ⁇ in the structure of the curing agent having a heteroatom is not particularly limited, but from the viewpoint of compatibility with the (A) epoxy resin, it is preferably 5 or more and 25 or less, and 5 or more and 20. The following are more preferable, and 5 or more and 15 or less are even more preferable.
  • the molecular weight ⁇ and the ratio ⁇ / ⁇ can be controlled within the numerical ranges described above by converting the molecular structure through a chemical reaction.
  • Epoxy resins include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenylbenzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin , diphenylsulfone-type epoxy resin, diphenyldisulfide-type epoxy resin, naphthalene-type epoxy resin, anthracene-type epoxy resin, hydroquinone-type epoxy resin, methylhydroquinone-type epoxy resin, dibutylhydroquino
  • epoxy resin or the like obtained by modifying these with isocyanate or the like can also be used together.
  • the above-mentioned epoxy resin is not particularly limited.
  • a combination with a type epoxy resin or the like can be preferably used.
  • the content of (A) the epoxy resin is not particularly limited, but is preferably 60% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 95% by mass or less, based on the liquid component of the epoxy resin composition. is 65% by mass or more and 90% by mass or less, more preferably 70% by mass or more and 85% by mass or less. (A) By setting the content of the epoxy resin within the above range, there is a tendency to obtain high adhesiveness.
  • the epoxy resin composition of the present embodiment contains (B) a curing agent having a heteroatom.
  • a curing agent having a heteroatom is a curing agent that satisfies the conditions of the molecular weight ⁇ and the ratio ⁇ / ⁇ described above.
  • the curing agent having a heteroatom is not particularly limited as long as it has a heteroatom, but it is preferably a curing agent having a heteroatom in its main chain.
  • the curing agent having a heteroatom in the main chain is not particularly limited, but from the viewpoint of functioning as a latent curing agent, a curing agent having a nitrogen atom or an oxygen atom in the main chain is preferable. in the main chain is more preferred.
  • the (B) curing agent having a heteroatom for example, the following amine imide compounds can be suitably used from the viewpoint of functioning as a latent curing agent.
  • the curing agent having a heteroatom is the following formula (1), (2) or ( It is preferable to contain the amine imide compound represented by 3) (hereinafter sometimes referred to as "the amine imide compound in the present embodiment").
  • each R 1 is independently a hydrogen atom, or a C 1 to 15 group optionally having a hydroxyl group, a carbonyl group, an ester bond, or an ether bond, represents a monovalent or n-valent organic group
  • R 2 and R 3 each independently represent an unsubstituted or substituted alkyl group, aryl group, aralkyl group having 1 to 12 carbon atoms, or R 2 and
  • Each R 4 independently represents a hydrogen atom or a monovalent or n-valent organic having 1 to 30 carbon atoms, which may contain an oxygen atom. represents a group
  • n represents an integer of 1 to 3.
  • the amine imide compound in the present embodiment is preferably a liquid compound at room temperature.
  • the viscosity at 25° C. can be used as an indicator of being “liquid at room temperature”.
  • the viscosity at 25 ° C. of the amine imide compound in the present embodiment is 1300 Pa s. or less, more preferably 900 Pa ⁇ s or less, still more preferably 800 Pa ⁇ s or less, and even more preferably 700 Pa ⁇ s or less.
  • the lower limit of the viscosity at 25°C is not particularly limited, it is preferably 0.01 Pa ⁇ s or more.
  • the viscosity of the amine imide compound in this embodiment can be controlled, for example, by adjusting the functional groups of R 1 to R 4 in formulas (1) to (3).
  • the viscosity (Pa s) of the amine imide compound at 25° C. in the present embodiment can be determined, for example, by dropping the amine imide compound (about 0.3 mL) into the measuring cup and measuring the sample temperature 15 minutes after reaching 25° C. It can be measured with an E-type viscometer (“TVE-35H” manufactured by Toki Sangyo Co., Ltd.).
  • n represents an integer of 1-3. From the viewpoint of adhesiveness of the epoxy resin composition of the present embodiment, n in the formulas (2) and (3) is preferably 2 or 3.
  • R 1 is each independently a hydrogen atom, or "a hydroxyl group, a carbonyl group, or an ester bond optionally having 1 to 1 carbon atoms. 15 monovalent or n-valent organic groups". Examples of such an organic group include, but are not limited to, "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", or " A group in which a part of carbon atoms constituting a hydrocarbon group is replaced with an ester bond or an ether bond".
  • hydrocarbon group examples include linear, branched, or cyclic alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and ethylhexyl group; alkenyl groups such as groups, propynyl groups, butynyl groups, pentynyl groups, hexynyl groups, octynyl groups, decynyl groups, dodecynyl groups, hexadecynyl groups, and octadecynyl groups; aryl groups such as phenyl groups; An aralkyl group consisting of a combination of an alkyl group such as a propylphenyl group and a phenyl group is exemplified.
  • the organic group represented by R 1 in the above formulas (1) to (3) may be unsubstituted or have a substituent.
  • substituents include, but are not limited to, halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azide groups, thiol groups, sulfo groups, nitro groups, hydroxy groups, acyl groups, and aldehyde groups. be done.
  • the organic group represented by R 1 in the above formulas (1) to (3) has 1 to 15 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 7 carbon atoms.
  • the number of carbon atoms in the organic group represented by R 1 is within the above range, the curing performance of the amine imide compounds of formulas (1) to (3) tends to be further improved.
  • the availability of raw materials for preparing formulas (1) to (3) is further improved.
  • the organic group represented by R 1 in formula (1) or (3) is preferably a group represented by formula (4) or (5) below.
  • the formula (1) or (3) has a group represented by the following formula (4) or (5) as R 1 , the curing performance of the amine imide compound tends to be further improved.
  • R 11 is each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms. and each n independently represents an integer of 0 to 6.
  • the number of carbon atoms in R 11 and n in the formula (4) or (5) are adjusted so that the maximum number of carbon atoms in the group represented by the formula (4) or (5) does not exceed 15. be done.
  • Examples of the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, the aryl group, or the aralkyl group having 7 to 9 carbon atoms for R 11 include the organic The same as those shown in the group can be mentioned.
  • the organic group represented by R 1 in the formula (2) is preferably a group represented by the following formula (6) or (7).
  • R 1 in the formula (2) it is easy to obtain a liquid amine imide compound at room temperature, and the curing performance of the amine imide compound tends to be further improved. It is in.
  • R 12 and R 13 each independently represent a single bond, an alkyl group having 1 to 5 carbon atoms, an aryl group, or an aralkyl group having 7 to 9 carbon atoms.
  • R 13 in the above formula (7) is preferably a single bond or a methyl group.
  • Examples of the alkyl group having 1 to 5 carbon atoms , aryl group, or aralkyl group having 7 to 9 carbon atoms for R 12 and R 13 are the organic groups represented by R 1 above. The same thing as a thing is mentioned.
  • R 2 and R 3 are each independently an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or represents a heterocyclic ring having 7 or less carbon atoms in which R 2 and R 3 are linked.
  • alkyl groups having 1 to 12 carbon atoms represented by R 2 or R 3 include, but are not limited to, methyl, ethyl, propyl, n-butyl, n-pentyl, and n-hexyl.
  • linear alkyl groups such as group, n-octyl group, n-decyl group, n-dodecyl group; isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-hexyl group, 2-octyl group, 2- branched alkyl groups such as 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 described above may be a combination of a linear alkyl group or a branched alkyl group and a cyclic alkyl group. Additionally, the alkyl groups described above may contain unsaturated bond groups.
  • the number of carbon atoms in the alkyl group represented by R 2 or R 3 is each independently 1-12, preferably 2-10, more preferably 5-10. From the viewpoint of handleability, it is preferable that the number of carbon atoms in the alkyl group represented by R 2 or R 3 is 2 or more. Further, by setting the number of carbon atoms in the alkyl group represented by R 2 or R 3 to 5 or more, the amine imide compound is likely to be liquid at room temperature, and the curability of the amine imide compound tends to be further improved.
  • Examples of the aryl group represented by R 2 or R 3 include, but are not limited to, phenyl group and naphthyl group.
  • examples of the aralkyl group represented by R 2 or R 3 include, but are not limited to, methylphenyl, ethylphenyl, methylnaphthyl, and dimethylnaphthyl groups.
  • at least one of R 2 and R 3 is preferably an aralkyl group, more preferably a methylphenyl group (benzyl group). This tends to further improve the curing performance of the amine imide compound.
  • the number of carbon atoms in the aryl group and aralkyl group represented by R 2 or R 3 is not particularly limited, it is preferably 6 or more and 20 or less.
  • Substituents for the alkyl group, aryl group, or aralkyl group represented by R 2 or R 3 are not limited to the following, but examples include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azide groups, thiol group, sulfo group, nitro group, hydroxy group, acyl group and aldehyde group.
  • R 2 and R 3 may combine to form a heterocyclic ring having 7 or less carbon atoms.
  • a hetero ring include, but are not limited to, a hetero ring formed by R 23 and N + in formula (1), (2) or (3), represented by formula (8) below.
  • R 23 represents a group in which R 2 and R 3 are linked.
  • R 23 represents a group forming a heterocyclic structure together with N + .
  • the hetero ring formed by R 23 and N + is not limited to the following, but examples thereof include 4-membered rings such as azetidine ring; 5-membered rings such as pyrrolidine ring, pyrrole ring, morpholine ring and thiazine ring; piperidine ring, etc. 6-membered ring; 7-membered ring such as hexamethyleneimine ring and azepine ring;
  • the hetero ring is preferably a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, or an azepine ring, and more preferably a 6-membered ring or a 7-membered ring.
  • examples of the substituents of the heterocyclic ring having 7 or less carbon atoms linked together include, but are not limited to, an alkyl group, an aryl group, or the above-described substituents for R 2 and R 3 .
  • the hetero ring has an alkyl group as a substituent, a methyl group bonded to the carbon atom adjacent to N + can be exemplified.
  • R 4 is each independently a hydrogen atom or “a monovalent or n-valent organic group”.
  • organic groups include, but are not limited to, "hydrocarbon group", "a hydrogen atom bonded to a carbon atom in a hydrocarbon group is replaced by a hydroxyl group, a carbonyl group, or a group containing a silicon atom. group”, or "a group in which a part of carbon atoms constituting a hydrocarbon group is replaced with an ester bond, an ether bond, or a silicon atom”.
  • hydrocarbon groups represented by R4 include, but are not limited to, straight groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and ethylhexyl group.
  • Chain, branched, or cyclic alkyl groups vinyl groups, propynyl groups, butynyl groups, pentynyl groups, hexynyl groups, octynyl groups, decynyl groups, dodecynyl groups, hexadecynyl groups, octadecynyl groups and other alkenyl groups; phenyl groups and the like an aryl group; or an aralkyl group consisting of a combination of an alkyl group such as a methylphenyl group, an ethylphenyl group and a propylphenyl group, and a phenyl group.
  • the hydrocarbon group represented by R4 includes 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, and a bisphenol F skeleton.
  • 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, and a bisphenol F skeleton.
  • examples of the organic group containing a bisphenol skeleton include, but are not limited to, groups in which a polyoxyalkylene group is added to the hydroxyl group of each bisphenol skeleton.
  • the organic group represented by R 4 in the formula (1) or (2) is preferably an alkyl group, an alkenyl group or an aralkyl group, more preferably an alkyl group or an alkenyl group, a branched alkyl group and More preferred are branched alkenyl groups.
  • these preferable groups may have a substituent. Having such a group tends to further improve the curing performance of the amine imide compound. Moreover, the glass transition temperature (Tg) of the cured product obtained using the amine imide tends to be further improved.
  • the organic group represented by R 4 has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • the carbon number of the organic group represented by R 4 is within the above range, the curing performance of the amine imide tends to be further improved.
  • the Tg of the cured product obtained using the amine imide compound is further improved, and the carbon number of the organic group represented by R 4 is within the above range, so that raw materials for preparing the amine imide compound are easily available. more improved.
  • R 4 in the formula (1) or (2) is a linear or branched C 3-12 alkyl group, or a linear or branched C 3-6 alkenyl groups are preferred. Having such a group tends to further improve the curing performance of the amine imide compound.
  • R 4 in the above formula (3) is preferably a group represented by the following formula (9) or (10). Having a group represented by the following formula (9) or (10) as R 4 in the formula (3) tends to further improve the curing performance of the amine imide compound.
  • R 41 and R 42 each independently represent an alkyl group, aryl group, or aralkyl group having 1 to 5 carbon atoms, and n each independently represents 0 Indicates an integer from ⁇ 10.
  • the epoxy resin composition of the present embodiment may contain a plurality of amine imide compounds represented by the formula (1), (2) or (3) as a curing agent. By including a plurality of amine imide compounds, it becomes possible to control the curing temperature and viscosity, and the effect of improving the properties can be obtained.
  • the epoxy resin composition of the present embodiment may contain a plurality of amineimide compounds having different structures, which are represented by the same formula among the amineimide compounds represented by the above formulas (1) to (3). good.
  • the amine imide composition may be obtained by mixing a plurality of amine imide compounds. It may be obtained by simultaneously producing a plurality of amine imides.
  • Method for producing an amine imide compound as (B) a curing agent having a heteroatom used in the epoxy resin composition of the present embodiment yields an amine imide compound having the structure of any one of the above formulas (1) to (3).
  • Methods for producing an amine imide composition include a method of mixing a plurality of amine imides obtained by the method described below, and a method of producing a mixture of a plurality of amine compounds at the same time.
  • One example of a method for producing an amine imide compound is a method having a reaction step of reacting an ester compound (BA), a hydrazine compound (BB), and a glycidyl ether compound (BC).
  • a method for producing an amine imide compound will be described below. Further, hereinafter, each compound (BA) to (BC) may be referred to as "component (BA), etc.”.
  • ester compound (BA) examples include, but are not limited to, monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, and cyclic esters.
  • monocarboxylic acid ester compound examples include, but are not limited to, methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, isokyl Methyl grass, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonate, methyl benzoylformate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxy benzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl and the like.
  • dicarboxylic acid ester compounds include, but are not limited to, 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 or the like may be used in place of these.
  • examples of cyclic esters include, but are not limited to, ⁇ -acetolactone, ⁇ -propionlactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone and the like.
  • diethyl esters, dipropyl esters, or the like may be used instead of these.
  • the ester compound (BA) is ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate.
  • the ester compound (BA) includes ethyl lactate, ethyl propionate, methyl mandelate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, and glutar. More preferred are dimethyl acid, dimethyl adipate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone and diethyl 1,3-acetonedicarboxylate.
  • the ester compound (BA) may be used alone or in combination of two or more.
  • hydrazine compounds include, but are not limited to, dimethylhydrazine, diethylhydrazine, methylethylhydrazine, methylpropylhydrazine, methylbutylhydrazine, methylpentylhydrazine, methylhexylhydrazine, ethylpropylhydrazine, ethylbutyl hydrazine, ethylpentylhydrazine, ethylhexylhydrazine, dipropylhydrazine, dibutylhydrazine, dipentylhydrazine, dihexylhydrazine, methylphenylhydrazine, ethylphenylhydrazine, methyltolylhydrazine, ethyltolylhydrazine, diphenylhydrazine, benzylphenylhydrazine, dibenzylhydrazine
  • hydrazine compound (BB) dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferable as the hydrazine compound (BB) from the viewpoint of curability and liquefaction. Furthermore, among these, dibenzylhydrazine and 1-aminopiperidine are more preferable in terms of availability and safety. Hydrazine compounds (BB) may be used alone or in combination of two or more.
  • glycidyl ether compound (BC) although not limited to the following, for example, a monofunctional monoglycidyl ether compound or a bifunctional or higher polyglycidyl ether compound can be used.
  • monoglycidyl ether compounds include, but are not limited to, 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
  • polyglycidyl ether compounds include, but are not limited to, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether.
  • glycidyl ether compounds include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t -butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, Hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bis
  • glycidyl ether compounds (BC) include n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether. , trimethylolpropane polyglycidyl ether, ethylene oxide addition type bisphenol A diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, and propylene oxide addition type bisphenol A diglycidyl ether are more preferred. Glycidyl ether compounds (BC) may be used alone or in combination of two or more.
  • the amounts of the ester compound (BA), hydrazine compound (BB), and glycidyl ether compound (BC) added to the reaction system for preparing the amine imide compound can be set based on the molar ratio of the functional groups. can.
  • the ester group of the ester compound (B-A) is preferably 0.8 mol to 3.0 mol, more preferably 0.9 mol to 1 mol of the primary amine of the hydrazine compound (B-B). It is 2.8 mol, more preferably 0.95 mol to 2.5 mol.
  • the glycidyl group of the glycidyl ether compound (BC) is preferably 0.8 mol to 2.0 mol, more preferably 0.8 mol to 2.0 mol, per 1 mol of the primary amine of the hydrazine compound (BB). It is 9 mol to 1.5 mol, more preferably 0.95 mol to 1.4 mol.
  • the amine imides represented by the above formulas (1) and (3) An amine imide composition containing the compound can be prepared at the same time.
  • the glycidyl group of the glycidyl ether compound (B-C) is preferably 0.1 mol to 3.0 mol, more preferably 1 mol of the primary amine of the hydrazine compound (B-B). It is 0.3 mol to 2.0 mol, more preferably 0.5 mol to 1.0 mol.
  • a solvent may be used from the viewpoint of uniformly progressing the reaction.
  • the solvent is not particularly limited as long as it does not react with the components (BA) to (BC).
  • examples include methanol, ethanol, 1-propanol, 2-propanol, butanol, t-butyl alcohol, and the like. alcohols; and ethers such as tetrahydrofuran and diethyl ether.
  • the reaction temperature of the components (BA) to (BC) is preferably 10 to 100°C, more preferably 40 to 90°C.
  • the reaction temperature is 10° C. or higher, the reaction tends to proceed faster and the purity of the resulting amine imide compound tends to be further improved.
  • the reaction temperature is 90° C. or lower, the polymerization reaction between the glycidyl ether compounds (BC) can be efficiently suppressed, so the purity of the amine imide compound tends to be further improved.
  • the reaction time of the components (B-A) to (B-C) is preferably 1 hour or more and 168 hours or less, more preferably 1 hour or more and 96 hours or more, and still more preferably 1 hour or more and 48 hours. less than an hour.
  • the obtained reactant can be purified by known purification methods such as washing, extraction, recrystallization, and column chromatography.
  • purification methods such as washing, extraction, recrystallization, and column chromatography.
  • the organic layer is heated under normal pressure or reduced pressure to remove unreacted raw materials and organic solvent from the reaction solution, thereby recovering the amine imide. be able to.
  • the amine imide compound can be recovered by purification by column chromatography.
  • the solvent used for the above washing is not particularly limited as long as it can dissolve the residue of the raw material, but from the viewpoint of yield, purity, and ease of removal, 1-hexane, 1-pentane, and cyclohexane are preferred.
  • the organic solvent used for the above extraction is not particularly limited as long as it can dissolve the desired amine imide compound. Isobutyl ketone is preferred, and ethyl acetate, chloroform, toluene and methyl isobutyl ketone are more preferred.
  • Well-known fillers such as alumina and silica gel can be used for column chromatography, and developing solvents include ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, and methyl isobutyl ketone. , acetonitrile, methanol, ethanol, isopropanol and the like can be used singly or in combination.
  • the epoxy resin composition of the present embodiment includes (B) a curing agent having a heteroatom, provided that the molecular weight of the curing agent and the number of heteroatoms in the structure of the curing agent are within a specific range, heteroatoms other than the above-mentioned amine imide compounds may be used.
  • heteroatom-containing curing agents include, but are not limited to, imidazoles, aliphatic amines, aromatic amines, amine-based curing agents such as polyamide resins; amide-based curing agents; acid anhydrides; phenolic curing agents such as phenols, polyhydric phenol compounds and modified products thereof, BF 3 -amine complexes, guanidine derivatives and the like. These curing agents may be used singly or in combination of two or more.
  • the total content of (B) the heteroatom-containing curing agent is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) the epoxy resin. , more preferably 1 to 40 parts by mass, and still more preferably 1 to 30 parts by mass.
  • the total content of the amine imide compound is, as described above, relative to the total amount of (A) the epoxy resin of 100 parts by mass. , preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, still more preferably 1 to 30 parts by mass.
  • the total content of the amine imide compound in the present embodiment is the total amount of (A) the epoxy resin. With respect to 100 parts by mass, it is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 1 to 15 parts by mass.
  • a curing agent having a heteroatom and a curing agent other than (B) the curing agent can be used in combination.
  • the curing agent having a heteroatom may function as a curing accelerator for other curing agents.
  • the total content of the curing agent having a heteroatom is based on the total amount of 100 parts by mass of the epoxy resin (A) , preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 1 to 15 parts by mass.
  • Curing agents other than the curing agent (B) that can be used in combination with the curing agent (B) having a heteroatom include, but are not limited to, the above-mentioned molecular weight ⁇ and the ratio ⁇ / ⁇ .
  • Amine-based curing agents such as imidazoles, aliphatic amines, aromatic amines, and polyamide resins; amide-based curing agents; acid anhydride-based curing agents such as acid anhydrides; Phenolic curing agents such as modified products, BF 3 -amine complexes, guanidine derivatives and the like can be mentioned. These other curing agents may be used singly or in combination of two or more.
  • the total content of (B) the curing agent having a heteroatom in the epoxy resin composition is preferably 0.4 mass from the viewpoint of achieving both reactivity and stability. % to 50% by mass. From the viewpoint of reactivity, it is more preferably 2.0% by mass or more, still more preferably 8.1% by mass or more, and even more preferably 9.0% by mass or more. From the viewpoint of storage stability, it is more preferably 40% by mass or less, still more preferably 25% by mass or less, and even more preferably 22% by mass or less.
  • the epoxy resin composition of this embodiment may contain an inorganic filler as needed.
  • an inorganic filler By using an inorganic filler, the low linear thermal expansion property of the resulting cured product can be enhanced.
  • inorganic fillers include, but are not limited to, fused silica, crystalline silica, alumina, talc, silicon nitride, and aluminum nitride.
  • the content of (C) the inorganic filler is preferably more than 5% by mass and not more than 98% by mass, more preferably It is 10% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less, and even more preferably 10% by mass or more and 87% by mass or less.
  • the epoxy resin composition of the present embodiment may optionally contain (D) a stabilizer.
  • (D) stabilizers include, but are not limited to, monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, and cyclic lactone compounds.
  • a compound represented by the following formula (A) or (B) can be used.
  • each of R 5 and R 6 is independently a hydrogen atom, or a 1 having 1 to 15 carbon atoms, optionally having a hydroxyl group, a carbonyl group, an ester bond or an ether bond. represents a valent or n-valent organic group, where n represents an integer of 2-3.
  • R 7 represents a monovalent or nvalent organic group having 1 to 15 carbon atoms, which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond, and n is 2. Represents an integer from ⁇ 3.
  • each of R 5 and R 6 is independently a hydrogen atom, or a “monovalent or an n-valent organic group”.
  • R 7 is "a monovalent or 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”. show.
  • organic groups are not limited to the following, but for example, the same as R 1 in the above formula (1), "hydrocarbon group”, "a hydrogen atom bonded to a carbon atom in the hydrocarbon group is a hydroxyl group or A group substituted with a carbonyl group”, or a "group in which a part of carbon atoms constituting a hydrocarbon group are replaced with an ester bond or an ether bond”.
  • Examples of the monocarboxylic acid ester compound as the stabilizer (D) include, but are not limited to, methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, methyl butyrate, and 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, and the like may be used instead of these.
  • dicarboxylic acid ester compound as the stabilizer (D) examples include, but are not limited to, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, and pimeline. dimethyl acid, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and 1 , diethyl 3-acetonedicarboxylate, and the like.
  • cyclic ester compound as the stabilizer (D) examples include, but are not limited to, ⁇ -acetolactone, ⁇ -propionlactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, and the like. .
  • diethyl esters, dipropyl esters, or the like may be used instead of these.
  • the epoxy resin composition of this embodiment may use stabilizers other than the stabilizers described above.
  • stabilizers include, but are not limited to, Lewis acid compounds, including boron, aluminum, gallium, indium, and the like, and acidic compounds such as carboxylic acids, phenols, and organic acids.
  • the content of (D) the stabilizer is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more, relative to 100 parts by mass of the (A) epoxy resin. It is from 1 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass.
  • the epoxy resin composition of the present embodiment may further contain other compounding agents such as curing accelerators, flame retardants, silane coupling agents, release agents, pigments, etc., if necessary.
  • compounding agents such as curing accelerators, flame retardants, silane coupling agents, release agents, pigments, etc.
  • suitable ones can be selected as appropriate.
  • flame retardants include, but are not limited to, halides, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds, and the like.
  • the cured product of this embodiment is a cured product obtained by curing the epoxy resin composition of this embodiment described above.
  • the cured product of the present embodiment can be obtained by thermally curing the epoxy resin composition described above, for example, by a conventionally known method.
  • the cured product of this embodiment can be obtained by the following method.
  • the above-mentioned (A) epoxy resin, (B) a curing agent having a heteroatom, and optionally (C) an inorganic filler, (D) a stabilizer, a curing accelerator, and/or a compounding agent etc. are sufficiently mixed using an extruder, a kneader, a roll or the like until uniform to obtain an epoxy resin composition.
  • the epoxy resin composition is cast, molded using 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, A cured product of the present embodiment can be obtained.
  • the cured product of the present embodiment can be obtained by the following method.
  • the epoxy resin composition described above is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. to obtain a solution.
  • a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper is impregnated with the obtained solution and dried by heating to obtain a prepreg.
  • a cured product can be obtained by subjecting the obtained prepreg to hot press molding.
  • the epoxy resin composition of the present embodiment and the cured product obtained therefrom can be used in various applications in which epoxy resins are used as materials.
  • encapsulants encapsulants formed from the cured product of the present embodiment
  • semiconductor encapsulants adhesives (adhesives containing the epoxy resin composition of the present embodiment), printed circuit board materials, paints, It is particularly useful for applications such as composite materials.
  • semiconductor sealing materials such as underfill and molding
  • conductive adhesives such as anisotropic conductive films (ACF)
  • printed wiring boards such as solder resists and coverlay films
  • glass fibers and carbon fibers etc. It is suitably used for composite materials such as impregnated prepregs.
  • An electronic member can be obtained using the cured product of the present embodiment described above.
  • Examples of the electronic member include, but are not limited to, semiconductor sealing materials such as underfill and molding, conductive adhesives such as ACF, printed wiring boards such as solder resists and coverlay films, glass fibers and carbon Composite materials such as prepreg made by impregnating fibers and the like can be mentioned.
  • an epoxy resin composition containing the compound of each synthesis example was prepared according to the examples described later. Then, various properties described later were measured for the obtained epoxy resin composition.
  • test pieces were prepared according to JISK6850.
  • an adherend an adherend (cold-rolled copper plate) conforming to JISC3141 and having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm was used.
  • An uncured test piece was placed in a small high-temperature chamber "ST-110B2" manufactured by ESPEC Co., Ltd. whose internal temperature was stable at 150° C., and heated for 2 hours to obtain a test piece for measuring shear bond strength.
  • test piece for measuring shear bond strength was removed from the small high-temperature chamber, left in a room temperature environment, and cooled to room temperature. After cooling to room temperature, using "AGX-5kNX” manufactured by Shimadzu Corporation, the maximum load at which the adhesive surface of the test piece breaks and the test piece separates is measured at a load cell of 5 kN and a speed of 5 mm / min, and separated. The shear bond strength was obtained by dividing the maximum load applied by the bond area. Based on the obtained shear adhesive strength, "adhesiveness" was evaluated based on the following criteria.
  • Shear adhesive strength A was 16.0 MPa ⁇ A.
  • Shear adhesive strength A was 13.5 MPa ⁇ A ⁇ 16.0 MPa.
  • Shear adhesive strength A was 10.0 MPa ⁇ A ⁇ 13.5 MPa.
  • x Shear adhesive strength A was A ⁇ 10 MPa.
  • the viscosity increase ratio was less than 1.75 times.
  • ⁇ The viscosity increase ratio was 1.75 times or more and less than 3 times.
  • x The viscosity increase ratio was 3 times or more.
  • the coefficient of thermal expansion was less than 50 ppm/°C.
  • ⁇ The thermal expansion coefficient was 50 ppm/°C or more and less than 70 ppm/°C.
  • ⁇ The coefficient of thermal expansion was 70 ppm/°C or more and less than 100 ppm/°C.
  • x The coefficient of thermal expansion was 100 ppm/°C or more. Or it cannot be measured.
  • Example 1 Put 10 g of epoxy resin (“EXA-830CRP” manufactured by DIC Corporation) and 3.0 g of compound A in a plastic stirring container, and stir and mix this with a rotation / revolution mixer (“ARE-310” manufactured by Thinky Co., Ltd.). to prepare an epoxy resin composition, evaluate "adhesiveness" by the above-mentioned evaluation method (1) for shear adhesion, and evaluate “storage stability at room temperature” by the above-mentioned evaluation method (2) for storage stability ” was evaluated, and the “linear thermal expansion property” was evaluated by the above-described evaluation method (3) for thermal expansion property.
  • EXA-830CRP manufactured by DIC Corporation
  • ARE-310 rotation / revolution mixer
  • Example 2 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound B, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 3 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound C, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 4 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound D, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 5 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound E, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated. Since the storage stability could not be measured due to the high viscosity of the compounded product, it is marked with "-" in the table below.
  • Example 6 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound F, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated. Since the storage stability could not be measured due to the high viscosity of the compounded product, it is marked with "-" in the table below.
  • Example 7 An epoxy resin composition was prepared in the same manner as in Example 1, except that compound A was changed to compound G, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 8 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound H, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 9 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound I, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 10 After kneading 10 g of epoxy resin (“EXA-830CRP” manufactured by DIC Corporation) and 0.7 g of silica filler (“SO-E2” manufactured by Admatec) with a triple roll (BR-150HCV manufactured by AIMEX), compound A 3.0 g together in a plastic stirring container, and stirred and mixed with a rotation/revolution mixer (“ARE-310” manufactured by Thinky Co., Ltd.) to prepare an epoxy resin composition, and the above-mentioned shear adhesive strength Evaluate "adhesiveness" by the evaluation method (1) above, evaluate “storage stability at room temperature” by the above-mentioned storage stability evaluation method (2), and evaluate the above-mentioned thermal linear expansion evaluation method (3) "Thermal linear expansion" was evaluated by.
  • EXA-830CRP manufactured by DIC Corporation
  • SO-E2 silica filler
  • BR-150HCV manufactured by Admatec
  • Example 11 An epoxy resin composition was prepared in the same manner as in Example 10, except that the amount of silica filler added was changed to 1.4 g, and the adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 12 An epoxy resin composition was prepared in the same manner as in Example 10, except that the amount of silica filler added was changed to 13.0 g, and the adhesion, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 13 An epoxy resin composition was prepared in the same manner as in Example 1 except that 0.7 g of ethyl propionate was added as a stabilizer, and adhesion, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 14 An epoxy resin composition was prepared in the same manner as in Example 1 except that 1.4 g of ethyl propionate was added as a stabilizer, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 15 An epoxy resin composition was prepared in the same manner as in Example 1 except that 0.7 g of ⁇ -butyrolactone was added as a stabilizer, and the adhesion, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 16 An epoxy resin composition was prepared in the same manner as in Example 1 except that 1.4 g of ⁇ -butyrolactone was added as a stabilizer, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 17 An epoxy resin composition was prepared in the same manner as in Example 1 except that 1.4 g of ethyl lactate was added as a stabilizer, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 18 An epoxy resin composition was prepared in the same manner as in Example 1 except that 1.4 g of dimethyl succinate was added as a stabilizer, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 19 An epoxy resin composition was prepared in the same manner as in Example 1, except that the amount of compound A added was changed to 1.0 g, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 20 Same as Example 1 except that the epoxy resin used was changed to 5.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 5.0 g of epoxy resin B ("jER630" manufactured by Mitsubishi Chemical Corporation). An epoxy resin composition was prepared in 1 and evaluated for adhesiveness, storage stability at room temperature, and linear thermal expansion.
  • epoxy resin A epoxy resin A
  • epoxy resin B jER630
  • Example 21 In the same manner as in Example 1, except that the epoxy resin used was changed to 5.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 5.0 g of epoxy resin C ("HP4032D” manufactured by DIC Corporation). An epoxy resin composition was prepared and evaluated for adhesion, storage stability at room temperature, and linear thermal expansion.
  • epoxy resin A epoxy resin A
  • HP4032D epoxy resin C
  • the epoxy resin to be used is 4.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 4.0 g of epoxy resin B ("jER630” manufactured by Mitsubishi Chemical Corporation) and 4.0 g of epoxy resin D (manufactured by Mitsubishi Chemical Corporation "JER1032H60”) 1.0 g and epoxy resin F (manufactured by Showa Denko Karenz Co., Ltd. "CDMDG”) 1.0 g was changed to prepare an epoxy resin composition in the same manner as in Example 1. Stability and linear thermal expansion were evaluated.
  • the epoxy resin to be used is 4.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 4.0 g of epoxy resin B ("jER630” manufactured by Mitsubishi Chemical Corporation) and 4.0 g of epoxy resin D (manufactured by Mitsubishi Chemical Corporation "JER1032H60") 1.0 g and epoxy resin G ("YX8000” manufactured by Mitsubishi Chemical Corporation) were changed to 1.0 g. Stability and linear thermal expansion were evaluated.
  • the epoxy resin to be used is 4.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 4.0 g of epoxy resin B ("jER630” manufactured by Mitsubishi Chemical Corporation) and 4.0 g of epoxy resin D (manufactured by Mitsubishi Chemical Corporation "jER1032H60") and 1.0 g of epoxy resin H (“YED216D” manufactured by Mitsubishi Chemical Corporation) were changed to 1.0 g. Stability and linear thermal expansion were evaluated.
  • the epoxy resin to be used is 4.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 4.0 g of epoxy resin B ("jER630” manufactured by Mitsubishi Chemical Corporation) and 4.0 g of epoxy resin E (manufactured by Mitsubishi Chemical Corporation " YX4000H”) and 1.0 g of epoxy resin I (“PETG” manufactured by Showa Denko Karenz Co., Ltd.) were changed to 1.0 g. Stability and linear thermal expansion were evaluated.
  • the epoxy resin to be used is 4.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation), 4.0 g of epoxy resin B ("jER630” manufactured by Mitsubishi Chemical Corporation) and 4.0 g of epoxy resin E (manufactured by Mitsubishi Chemical Corporation "YX4000H”) 1.0 g and epoxy resin J (manufactured by Nagase ChemteX Corporation "EX-321L”) 1.0 g was changed to prepare an epoxy resin composition in the same manner as in Example 1. was evaluated for storage stability and linear thermal expansion.
  • Example 27 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound J, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 28 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound K, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 29 An epoxy resin composition was prepared in the same manner as in Example 10, except that compound A was changed to compound K, the silica filler was changed to "SE2200-SEJ" manufactured by Admatec, and the amount of silica filler added was changed to 19.5 g. Then, adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 30 An epoxy resin composition was prepared in the same manner as in Example 24, except that the silica filler was changed to "SE205-SEJ" manufactured by Admatec, and adhesion, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 31 An epoxy resin composition was prepared in the same manner as in Example 24, except that the silica filler was changed to "SE203-SEJ" manufactured by Admatec, and adhesion, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 32 An epoxy resin composition was prepared in the same manner as in Example 24, except that the silica filler was changed to "SE1050-SET” manufactured by Admatec, and adhesion, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 33 An epoxy resin composition was prepared in the same manner as in Example 24, except that the amount of silica filler added was changed to 30.0 g, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 34 An epoxy resin composition was prepared in the same manner as in Example 24, except that the amount of silica filler added was changed to 39.0 g, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 35 An epoxy resin composition was prepared in the same manner as in Example 24 except that the silica filler used was 31.0 g of "SE2200-SEJ” manufactured by Admatechs and 46.0 g of "FB-5D” manufactured by Denka. , storage stability at room temperature, and linear thermal expansion.
  • Example 36 Example 24 except that 36.0 g of "SE2200-SEJ” manufactured by Admatechs and 57.0 g of "FB-5D” manufactured by Denka were used as silica fillers, and 1.4 g of ⁇ -butyrolactone was added as a stabilizer.
  • An epoxy resin composition was prepared in the same manner, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 37 The epoxy resin used was changed to 6.0 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 4.0 g of epoxy resin H ("YED216D” manufactured by Mitsubishi Chemical Corporation), and the silica filler used was Admatechs. 49.0 g of "SE2200-SEJ” manufactured by Denka Co., Ltd., 81.0 g of "FB-5D” manufactured by Denka Co., Ltd., and 1.4 g of ⁇ -butyrolactone was added as a stabilizer. It was prepared and evaluated for adhesion, storage stability at room temperature, and linear thermal expansion.
  • Example 38 The epoxy resin to be used was changed to 0.6 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 0.4 g of epoxy resin H ("YED216D” manufactured by Mitsubishi Chemical Corporation), and the silica filler used was changed to an average particle size.
  • An epoxy resin composition was prepared in the same manner as in Example 24 except that 27.4 g of NdFeB alloy magnetic powder with a diameter of 100 ⁇ m was used and 0.14 g of ⁇ -butyrolactone was added as a stabilizer. Stability and linear thermal expansion were evaluated.
  • Example 39 The epoxy resin to be used was changed to 0.6 g of epoxy resin A ("EXA-830CRP” manufactured by DIC Corporation) and 0.4 g of epoxy resin H ("YED216D” manufactured by Mitsubishi Chemical Corporation), and the silica filler used was changed to an average particle size.
  • An epoxy resin composition was prepared in the same manner as in Example 24 except that 70.6 g of NdFeB alloy magnetic powder with a diameter of 100 ⁇ m was used and 0.14 g of ⁇ -butyrolactone was added as a stabilizer. Stability and linear thermal expansion were evaluated.
  • Example 40 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound L, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 41 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound M, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 42 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound N, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 43 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound O, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 44 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound P, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 45 An epoxy resin composition was prepared in the same manner as in Example 1 except that compound A was changed to compound Q, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 46 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.25 g of Compound A and 0.75 g of Compound E, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 47 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.0 g of Compound B and 1.0 g of Compound E, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 48 An epoxy resin composition was prepared in the same manner as in Example 1, except that Compound A was changed to 1.0 g of Compound B, 1.0 g of Compound F, and 1.0 g of Compound N. evaluated the sex.
  • Example 49 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.25 g of Compound J and 0.75 g of Compound M, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 50 An epoxy resin composition was prepared in the same manner as in Example 1, except that Compound A was changed to 2.0 g of Compound J and 1.0 g of Compound Q, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 51 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.25 g of Compound K and 0.75 g of Compound N, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 52 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.5 g of Compound L and 0.5 g of Compound N, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 53 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.0 g of Compound L and 1.0 g of Compound Q, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 54 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.25 g of Compound K and 0.75 g of Compound P, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 55 An epoxy resin composition was prepared in the same manner as in Example 1 except that Compound A was changed to 2.25 g of Compound K and 0.75 g of Compound Q, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 56 Epoxy resin in the same manner as in Example 1, except that Compound A was changed to 0.975 g of Compound A, 0.325 g of Compound E, and 2.6 g of curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane). A composition was prepared and evaluated for adhesion, storage stability at room temperature, and linear thermal expansion.
  • Example 57 Compound A was changed to 0.975 g of compound A, 0.325 g of compound E, 2.6 g of curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane), and 13.0 g of silica filler. , an epoxy resin composition was prepared in the same manner as in Example 10, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 58 Compound A was changed to 0.975 g of compound J, 0.325 g of compound M, 2.6 g of curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane), and 13.0 g of silica filler. , an epoxy resin composition was prepared in the same manner as in Example 10, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 59 Compound A was changed to 0.975 g of compound K, 0.325 g of compound N, 2.6 g of curing agent A (4,4'-diamino-3,3'-diethyldiphenylmethane), and 13.0 g of silica filler. , an epoxy resin composition was prepared in the same manner as in Example 10, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 60 Example 10 except that the compound A was changed to 0.693 g of compound A, 0.231 g of compound E, 1.8 g of curing agent B (liquid aromatic amine having a diaminodiphenylmethane skeleton), and 13.0 g of silica filler.
  • An epoxy resin composition was prepared in the same manner, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 61 Compound A was the same as in Example 10, except that 0.693 g of compound J, 0.231 g of compound M, 1.8 g of curing agent B (liquid aromatic amine having a diaminodiphenylmethane skeleton), and 13.0 g of silica filler were added.
  • An epoxy resin composition was prepared in the same manner, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 62 Compound A was the same as in Example 10, except that 0.693 g of compound K, 0.231 g of compound N, 1.8 g of curing agent B (liquid aromatic amine having a diaminodiphenylmethane skeleton), and 13.0 g of silica filler were added.
  • An epoxy resin composition was prepared in the same manner, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Example 2 An epoxy resin composition was prepared in the same manner as in Example 1, except that the compound A was changed to 2.8 g of the curing agent B (a liquid aromatic amine having a diaminodiphenylmethane skeleton), and the adhesion, storage stability at room temperature, Thermal linear expansion was evaluated.
  • the curing agent B a liquid aromatic amine having a diaminodiphenylmethane skeleton
  • Compound A was changed to 9.3 g of curing agent C ("HN5500” manufactured by Showa Denko Materials Co., Ltd.), and 2E4MZ (2-ethyl-4-methylimidazole) was added as a curing accelerator.
  • An epoxy resin composition was prepared in the same manner as in Example 1, and adhesiveness, storage stability at room temperature, and linear thermal expansion were evaluated.
  • Curing agent C is an acid anhydride and has a molecular weight ⁇ of 168.
  • composition and evaluation results of each example and comparative example are shown in the table below.
  • the liquid aromatic amines used in Comparative Examples 1 and 2 and the acid anhydride used in Comparative Example 3 were inferior in adhesiveness, respectively, and in Comparative Examples 1 and 2, storage stability was also inferior. was confirmed.
  • Comparative Example 4 it was found that when the ratio ⁇ / ⁇ of the curing agent is less than 30, the adhesion and thermal linear expansion properties are poor.
  • the addition of the inorganic filler exhibited excellent low linear thermal expansion properties.
  • the storage stability was further improved by adding a stabilizer having a specific structure.
  • the epoxy resin composition of the present invention can be used for sealing materials, adhesives, printed circuit board materials, paints, composite materials, semiconductor sealing materials such as underfills and moldings, conductive adhesives such as ACF, solder resists and coverlays. It has industrial applicability as a printed wiring board such as a film, or as a composite material such as a prepreg impregnated with glass fiber or carbon fiber.

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WO2025028598A1 (ja) * 2023-08-01 2025-02-06 旭化成株式会社 エポキシ樹脂用硬化剤、エポキシ樹脂組成物、硬化物、封止材及び接着剤
WO2025028611A1 (ja) * 2023-08-01 2025-02-06 旭化成株式会社 エポキシ樹脂用硬化剤、エポキシ樹脂組成物、硬化物、封止材及び接着剤
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WO2025028605A1 (ja) * 2023-08-01 2025-02-06 旭化成株式会社 硬化剤、エポキシ樹脂組成物、硬化物、封止材及び接着剤
WO2025028598A1 (ja) * 2023-08-01 2025-02-06 旭化成株式会社 エポキシ樹脂用硬化剤、エポキシ樹脂組成物、硬化物、封止材及び接着剤
WO2025028611A1 (ja) * 2023-08-01 2025-02-06 旭化成株式会社 エポキシ樹脂用硬化剤、エポキシ樹脂組成物、硬化物、封止材及び接着剤
TWI910752B (zh) * 2023-08-01 2026-01-01 日商旭化成股份有限公司 環氧樹脂用硬化劑、環氧樹脂組合物、硬化物、密封材料及接著劑
TWI910751B (zh) * 2023-08-01 2026-01-01 日商旭化成股份有限公司 硬化劑、環氧樹脂組合物、硬化物、密封材料及接著劑
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