WO2022107678A1 - Résine époxyde, composition de résine durcissable et objet durci obtenu à partir de celle-ci - Google Patents

Résine époxyde, composition de résine durcissable et objet durci obtenu à partir de celle-ci Download PDF

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WO2022107678A1
WO2022107678A1 PCT/JP2021/041534 JP2021041534W WO2022107678A1 WO 2022107678 A1 WO2022107678 A1 WO 2022107678A1 JP 2021041534 W JP2021041534 W JP 2021041534W WO 2022107678 A1 WO2022107678 A1 WO 2022107678A1
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epoxy resin
resin composition
epoxy
formula
represented
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PCT/JP2021/041534
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English (en)
Japanese (ja)
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隆行 遠島
健一 窪木
正人 鎗田
政隆 中西
裕介 川野
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日本化薬株式会社
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Priority to KR1020237009096A priority Critical patent/KR20230107539A/ko
Priority to CN202180063925.9A priority patent/CN116234851A/zh
Publication of WO2022107678A1 publication Critical patent/WO2022107678A1/fr

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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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3227—Compounds containing acyclic nitrogen atoms
    • 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

Definitions

  • the present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product thereof.
  • epoxy resin By curing with various curing agents, epoxy resin becomes a cured product with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and becomes an adhesive, paint, laminated board, molding material, note. It is used in a wide range of fields such as mold materials.
  • Carbon fiber reinforced composite material (CFRP) which is made by impregnating reinforced fibers with an epoxy resin and a curing agent as a matrix resin and curing them, can impart properties such as weight reduction and high strength.
  • CFRP Carbon fiber reinforced composite material
  • Materials such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and tetraglycidyldiaminodiphenylmethane are generally used as resins used for matrix resins such as CFRP, and glycidylamine type epoxy resins are used for aircraft applications. Materials such as tetraglycidyldiaminodiphenylmethane are used.
  • Patent Document 1 the required characteristics for CFRP have become stricter, and when applied to aerospace applications and structural materials such as vehicles, heat resistance of 180 ° C or higher is required.
  • the glycidylamine-based material has high heat resistance, it has a high water absorption rate and has a problem of deterioration of characteristics after water absorption.
  • a general glycidyl ether type epoxy resin has a problem that its elastic modulus is low although its water absorption rate is relatively low. Therefore, there is a demand for a material that satisfies high heat resistance, high elastic modulus, and low water absorption.
  • an object of the present invention is to provide an epoxy resin or an epoxy resin composition whose cured product has high heat resistance, high elastic modulus and low water absorption.
  • the present invention relates to the following [1] to [8].
  • n is the number of repetitions, and the average value thereof is 1 ⁇ n ⁇ 5.
  • n is the number of repetitions, and the average value thereof is 1 ⁇ n ⁇ 5.
  • the present invention relates to an epoxy resin having a specific structure, a curable resin composition and a cured product thereof, and the cured product has high heat resistance, high elastic modulus and low water absorption. Therefore, the present invention is used for insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulation materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials such as CFRP, adhesives, paints, etc. It is useful.
  • the GPC chart of synthesis example 1 is shown.
  • the 1H-NMR chart of synthesis example 1 is shown.
  • the HPLC chart of synthesis example 1 is shown.
  • the GPC chart of Example 1 is shown.
  • the 1H-NMR chart of Example 1 is shown.
  • the HPLC chart of Example 1 is shown.
  • the GPC chart of Reference Example 1 is shown.
  • the 1H-NMR chart of Reference Example 1 is shown.
  • the HPLC chart of Reference Example 1 is shown.
  • an aromatic amine resin represented by the following formula (6) can be used as a precursor.
  • n is the number of repetitions, and the average value thereof is 1 ⁇ n ⁇ 5.
  • the aromatic amine resin represented by the formula (6) is more preferably represented by the following formula (7). This is because the crystallinity of the benzene ring to which the amino group is not bonded in the formula (6) is lower than that in the ortho-position or the para-position. The decrease in crystallinity increases the solvent stability and facilitates the preparation of the resin solution. In addition, the crystallinity of the compound derived from this can be reduced. Therefore, it is possible to suppress the precipitation of crystals during storage after the composition.
  • n is the number of repetitions, and the average value thereof is 1 ⁇ n ⁇ 5.
  • the method for producing the aromatic amine resin represented by the formula (6) or the formula (7) is not particularly limited.
  • the above formula is obtained by reacting aniline with m-dissopropenylbenzene or m-di ( ⁇ -hydroxyisopropyl) benzene at 180 to 250 ° C. in the presence of an acidic catalyst.
  • the acidic catalyst used for synthesizing the aromatic amine resin represented by the formula (6) is hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, and methanesulfonic acid. Acids, active white clay, ion exchange resin and the like can be mentioned. These may be used alone or in combination of two or more.
  • the amount of the catalyst used is 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the aniline used. If the amount is too large, the viscosity of the reaction solution becomes too high and stirring becomes difficult, and the amount is too small. And the progress of the reaction slows down.
  • the reaction may be carried out using an organic solvent such as toluene or xylene, or may be carried out without a solvent.
  • an organic solvent such as toluene or xylene
  • the reaction may be carried out without a solvent.
  • an organic solvent such as toluene or xylene
  • the reaction may be carried out without a solvent.
  • an organic solvent such as toluene or xylene
  • the reaction may be carried out using an organic solvent such as toluene or xylene, or may be carried out without a solvent.
  • an organic solvent such as toluene or xylene
  • the reaction may be carried out without a solvent.
  • the diphenylamine derivative is added to 1% by weight or less, preferably 0.5% by weight or less under high temperature and high vacuum, or by means such as steam distillation. , More preferably to 0.2% by weight or less.
  • the epoxy resin of the present invention is represented by the following formula (1), and the total content of the epoxy resins represented by the following formulas (2) to (4) is represented by the following formula (1). It is 80 area% or less in the resin.
  • n is the number of repetitions, and the average value thereof is 1 ⁇ n ⁇ 5.
  • n is preferably 1 ⁇ n ⁇ 5, and more preferably 1 ⁇ n ⁇ 3.
  • the total content of the epoxy resins represented by the formulas (2) to (4) in the epoxy resin represented by the formula (1) is two, gel permeation chromatography analysis and high performance liquid chromatography analysis. It can be obtained by an analysis method using. In the present invention, the analysis was performed under the following conditions.
  • the content ( ⁇ 2 to ⁇ 4) of the epoxy resin represented by the formulas (2) to (4) contained in the above can be determined. Therefore, for example, the product of ⁇ and ⁇ 2 is the content of the epoxy resin represented by the formula (2) contained in the epoxy resin represented by the formula (1).
  • the epoxy resin of the present invention preferably has a total content of the epoxy resins represented by the formulas (2) to (4) in the epoxy resin represented by the formula (1) of 80 area% or less. It is more preferably 70 area% or less, and most preferably 60 area% or less. This is because if the area is 80 area% or less, the orientation and the molecular weight distribution are controlled, and at the same time, an epoxy resin having high heat resistance, low water absorption, and high elastic modulus, which are difficult to develop, can be obtained. ..
  • the lower limit may be 0 area%, but is preferably 20 area% or more, and more preferably 40 area% or more.
  • the lower limit may be 0 area%, but is preferably 20 area% or more, and more preferably 40 area% or more.
  • the epoxy resin represented by the above formula (1) is more preferably represented by the following formula (5). This is because each isopropylidene structure and cross-linking points are closer to each other, so that the rigidity of the molecule is improved due to the steric hindrance, and high elastic modulus and low water absorption are easily exhibited.
  • n and the preferable range are the same as those in the formula (1).
  • the method for producing the epoxy resin of the present invention is not particularly limited, but it can be obtained, for example, by adding or ring-closing the aromatic amine resin represented by the above formula (6) and epihalohydrin in the presence of a solvent and a catalyst.
  • the amount of epihalohydrin used is usually 3.0 to 20.0 mol, preferably 3.5 to 10.0 mol, relative to 1 mol of the amino group of the amine compound.
  • Examples of the alkali metal hydroxide that can be used in the epoxidation reaction include sodium hydroxide and potassium hydroxide.
  • the alkali metal hydroxide may be a solid substance or an aqueous solution thereof may be used.
  • an aqueous solution is used, the aqueous solution of the alkali metal hydroxide is continuously added into the reaction system, and water and epihalohydrin are continuously distilled under reduced pressure or under normal pressure, and further separated to remove water.
  • a method of continuously returning epihalohydrin into the reaction system may be used.
  • the amount of the alkali metal hydroxide used is usually 0.9 to 2.5 mol, preferably 0.95 to 1.5 mol, based on 1 mol of the amino group of the amine compound.
  • a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst.
  • the amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, based on 1 mol of the amino group of the amine compound. If the amount used is too small, a sufficient reaction promoting effect cannot be obtained, and if the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin increases, which may cause deterioration of electrical reliability.
  • alcohols such as methanol, ethanol and isopropyl alcohol
  • an aprotonic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane
  • the amount used is usually 2 to 50% by weight, preferably 4 to 20% by weight, based on the amount of epihalohydrin used.
  • an aprotic polar solvent it is usually 5 to 100% by weight, preferably 10 to 80% by weight, based on the amount of epihalohydrin used.
  • the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C.
  • the reaction time is usually 0.5 to 100 hours, preferably 1 to 30 hours.
  • the reaction product is washed with water, or without washing with water, the epihalohydrin, solvent, etc. are removed under heating and reduced pressure.
  • the recovered epoxy resin is dissolved in a solvent such as toluene and methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide is added. It is also possible to carry out a reaction to ensure ring closure.
  • the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the amino group of the amine compound used for glycidylation.
  • the reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 24 hours.
  • the produced salt is removed by filtration, washing with water, or the like, and the solvent is further distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.
  • the epoxy resin of the present invention is usually in the form of a liquid to solid resin at room temperature, and its softening point is preferably 100 ° C. or lower, more preferably 80 ° C. or lower. When the softening point is higher than 100 ° C., the viscosity is high and the fiber impregnation is reduced during the preparation of the prepreg.
  • the epoxy equivalent is preferably 142 to 1000 g / eq, more preferably 150 to 500 g / eq, particularly preferably 170 to 450 g / eq, and most preferably 180 to 400 g / eq.
  • the epoxy resin represented by the formula (1) can be used alone or in combination with other epoxy resins.
  • the proportion of the epoxy resin represented by the formula (1) in the total epoxy resin is preferably 10 to 98% by weight, more preferably 20 to 95% by weight, still more preferably 30 to 95% by weight. %.
  • Examples of the curing agent that can be used in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of the curing agent that can be used include, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diamino.
  • Aromatic amine compounds such as the aromatic amine compound described in 1 and Synthesis Example 2, 1,3-bis (aminomethyl) cyclohexane, isophorondiamine, 4,4'-methylenebis (cyclohexylamine), norbornandiamine, ethylenediamine, propane.
  • Examples thereof include aliphatic diamines such as diamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, dimerdiamine and triethylenetetramine, but the present invention is not limited to this and may be suitably used depending on the characteristics desired to be imparted to the composition. can.
  • an aromatic amine it is preferable to use an aromatic amine to secure the pot life, and it is preferable to use an aliphatic amine when it is desired to impart immediate curability.
  • an amine compound containing a bifunctional component as a main component as a curing agent, a highly linear network can be constructed during the curing reaction, and particularly excellent toughness can be exhibited.
  • amide compounds such as polyamide resin synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro.
  • Acid anhydride compounds such as phthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols ( Phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.
  • bisphenols bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.
  • aldehydes formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphtho
  • aldehyde glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc., or the phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroinden, divinylbenzene).
  • the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin. Good cured physical properties can be obtained by setting the amount to 0.5 to 1.5 equivalents.
  • a curing accelerator When performing a curing reaction using the above curing agent, a curing accelerator may be used in combination.
  • the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethyl imidazole, 2-phenyl imidazole, and 2-ethyl-4-methyl imidazole, 2- (dimethylaminomethyl) phenol, and triethylenediamine.
  • Triethanolamine such as 1,8-diazabicyclo (5,4,0) undecene-7
  • organic phosphines such as triphenylphosphine, diphenylphosphine, tributylphosphine, metal compounds such as tin octylate, Tetra-substituted phosphonium-tetra-substituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, tetras such as N-methylmorpholin / tetraphenylborate, etc.
  • Examples thereof include carboxylic acid compounds such as phenylboron salt, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid and salicylic acid.
  • a carboxylic acid compound such as salicylic acid is preferable from the viewpoint of accelerating the curing reaction between the amine compound and the epoxy resin.
  • the curing accelerator 0.01 to 15 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.
  • an inorganic filler can be added to the epoxy resin composition of the present invention as needed.
  • the inorganic filler include powders such as crystalline silica, molten silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, and talc, or these.
  • powders such as crystalline silica, molten silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, and talc, or these.
  • examples thereof include, but are not limited to, spherical beads and the like. These may be used alone or may use two or more kinds.
  • the amount of these inorganic fillers used varies depending on the application, but when used for semiconductor encapsulants, for example, the cured product of the epoxy resin composition has heat resistance, moisture resistance, mechanical properties, flame retardancy, etc. From the surface, it is preferably used in a proportion of 20% by weight or more in the epoxy resin composition, more preferably 30% by weight or more, and particularly 70 to 95% by weight in order to improve the linear expansion coefficient with the lead frame. It is more preferable to use it in a proportion.
  • the epoxy resin composition of the present invention can be blended with a mold release agent in order to improve the mold release from the mold at the time of molding.
  • a mold release agent can be used, but for example, ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and partiminic acid, metal salts thereof, and polyolefins such as polyethylene oxide and non-polyethylene oxide. Examples include waxes. These may be used alone or in combination of two or more.
  • the blending amount of these release agents is preferably 0.5 to 3% by weight based on the total organic components. If it is less than this, the mold release from the mold will be poor, and if it is too large, the adhesion to the lead frame or the like will be poor.
  • a coupling agent can be added to the epoxy resin composition of the present invention in order to enhance the adhesiveness between the inorganic filler and the resin component.
  • the coupling agent any conventionally known one can be used, and for example, vinylalkoxysilane, epochionicsilane, styrylalkoxysilane, methacryoxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and isocyanatoalkoxy can be used.
  • Examples thereof include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelate. These may be used alone or in combination of two or more.
  • the surface of the inorganic filler may be treated with the coupling agent in advance and then kneaded with the resin, or the coupling agent may be mixed with the resin and then the inorganic filler may be kneaded. ..
  • a known additive can be added to the epoxy resin composition of the present invention, if necessary.
  • the additives include polybutadiene and modified products thereof, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide-based compound, cyanate ester-based compound, silicone gel, and silicone oil.
  • colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
  • the epoxy resin composition of the present invention is obtained by uniformly mixing each of the above components.
  • the epoxy resin composition of the present invention can be easily obtained as a cured product by the same method as a conventionally known method.
  • the epoxy resin and the curing agent, and if necessary, the curing accelerator, the inorganic filler, the mold release agent, the silane coupling agent, and the additive are uniformly used using an extruder, a kneader, a roll, or the like as necessary.
  • the epoxy resin composition of the present invention is obtained by sufficiently mixing, and this is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, etc., and further at 80 to 200 ° C. for 2 to 10 hours.
  • a cured product can be obtained by heating to.
  • the epoxy resin composition of the present invention may contain a solvent, if necessary.
  • the epoxy resin composition (epoxy resin varnish) containing a solvent is impregnated with a fibrous substance (base material) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and heated and dried to obtain prepreg. By press molding, a cured product of the epoxy resin composition of the present invention can be obtained.
  • the solvent content of this epoxy resin composition is usually about 10 to 70% by weight, preferably about 15 to 70% by weight by internal division.
  • solvent examples include ⁇ -butyrolactones, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone and other amide solvents; Ethereal solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, preferably lower (1 to 3 carbon atoms) alkylene glycol mono or di-lower (1 carbon number) ⁇ 3) Alkyl ether; Ketone-based solvent such as methyl ethyl ketone and methyl isobutyl ketone, preferably di-lower (1 to 3 carbon atoms) alkyl ketone in which two alkyl groups may be the same or different; aromatic-based such as toluene and xylene. Examples include solvents. These may be alone or may be
  • a sheet-shaped adhesive (sheet of the present invention) can be obtained by applying the epoxy resin varnish on the release film, removing the solvent under heating, and performing B-stage formation.
  • This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
  • thermosetting resins such as epoxy resins are used are mentioned, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed circuit boards, etc.). (Including wire coating, etc.), sealants, additives to other resins, etc. can be mentioned.
  • adhesives for civil engineering, construction, automobiles, general office work, medical use examples include adhesives for electronic materials.
  • adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, and anisotropic conductive films (these are adhesives).
  • ACF an adhesive for mounting such as an anisotropic conductive paste (ACP) and the like can be mentioned.
  • Sealants include potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, dipping, transfer mold encapsulation, potting encapsulation for ICs, COBs, COFs, TABs, etc., and flip chips. Examples include underfilling for IC packages such as QFP, BGA, and CSP, and sealing (including reinforcing underfilling) when mounting IC packages.
  • the present invention will be described in more detail by way of examples, but in the following, the parts are parts by weight unless otherwise specified.
  • the present invention is not limited to these examples.
  • the epoxy equivalent was measured by a method according to JIS K-7236, and the softening point was measured by a method according to JIS K-7234.
  • the extracted toluene and water were returned to the system, and 88 parts of a 30% sodium hydroxide aqueous solution was added for neutralization. Then, the organic layer was washed with water and concentrated until the waste liquid became neutral to obtain 458 parts of the aromatic amine resin (A1).
  • the amine equivalent of the aromatic amine resin (A1) was 185 g / eq, and the softening point was 58.7 ° C.
  • Example 1 186 parts of aromatic amine resin (A1), 555 parts of epichlorohydrin, 55 parts of methanol, 5 parts of water obtained in Synthesis Example 1 while performing nitrogen purging on a flask equipped with a thermometer, a cooling tube, a fractionation tube and a stirrer. .5 parts were added and reacted at 77 ° C. for 8 hours. The internal temperature was cooled to 65 ° C., and 81 parts of sodium hydroxide was added in portions over 90 minutes. The reaction was continued at 65 ° C. for 3 hours, 500 parts of water was added, sodium chloride in the organic layer was removed, and the mixture was concentrated under reduced pressure at 120 ° C.
  • HPLC analysis measure wavelength: 274 nm
  • 2,2'-(1,3-phenylenedisopropridene) bis (1,3-phenylenedisopropyridene) in n 1 body.
  • Diglycidylaniline) is 31.2 area%
  • 2,4'-(1,3-phenylenedisopropyridene) bis diglycidylaniline
  • 4,4'-(1,3-phenylene) Disopropyridene) bis (diglycidyl aniline) was 33.0 area%.
  • each isopropridene bond among the epoxy resins represented by the 2,2'-(1,3-phenylenedisopropyridene) bis (diglycidylaniline) (formula (2)) contained in EP1 is in the meta position.
  • (Replaced) is 19.0 area%
  • each isopropylidene bond is (Replaced with meta position) is 19.7 area%
  • 4,4'-(1,3-phenylenedisopropyridene) bis (diglycidylaniline) each isopropi among the epoxy resins represented by the formula (4)).
  • (Reden bond replaced with meta position) was 20.1 area%.
  • Example 2 Comparative Examples 1 and 2] Epoxy resins (EP1, EP2) and epoxy resins (EP3; RE-304S, manufactured by Nippon Kayaku Co., Ltd.) obtained in Example 1 and Reference Example 1, and 4,4'-methylenebis (2,) as a curing agent.
  • 6-Diethylaniline manufactured by Tokyo Kasei Co., Ltd., abbreviation: MDEA
  • MDEA Methylaniline
  • Table 1 shows the results of measuring the evaluation test pieces under the following conditions.
  • Example 2 had high heat resistance, high bending strength, high elastic modulus, and low water absorption.
  • the epoxy resin of the present invention is an insulating material for electrical and electronic parts (highly reliable semiconductor encapsulation material, etc.), a laminated board (printed wiring board, BGA board, build-up board, etc.), and an adhesive (conductive adhesive, etc.). It is useful for various composite materials such as CFRP and paints, and is particularly useful for various composite material applications such as CFRP that strongly require high elasticity.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une résine époxyde et une composition de résine époxyde qui donnent des objets durcis ayant une résistance élevée à la chaleur, un module élevé et une faible absorption d'eau.　La résine époxyde est représentée par la formule (1), et a une teneur totale en résines époxydes représentées respectivement par les formules (2) à (4) de 80 % en surface ou moins. (Dans la formule (1), n est le nombre de répétitions et la moyenne de celles-ci est 1<n<5.)
PCT/JP2021/041534 2020-11-19 2021-11-11 Résine époxyde, composition de résine durcissable et objet durci obtenu à partir de celle-ci WO2022107678A1 (fr)

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KR1020237009096A KR20230107539A (ko) 2020-11-19 2021-11-11 에폭시 수지, 경화성 수지 조성물, 및 그 경화물
CN202180063925.9A CN116234851A (zh) 2020-11-19 2021-11-11 环氧树脂、硬化性树脂组合物、及其硬化物

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JPS62155242A (ja) * 1985-12-27 1987-07-10 Mitsui Petrochem Ind Ltd ビス（ｐ−アミノクミル）ベンゼン類の製造方法
JPS62155241A (ja) * 1985-12-27 1987-07-10 Mitsui Petrochem Ind Ltd ビス（ｐ−アミノクミル）ベンゼン類の製造方法
JPS62260819A (ja) * 1986-01-22 1987-11-13 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 熱硬化性組成物
JPH01215822A (ja) * 1987-12-31 1989-08-29 Shell Internatl Res Maatschappij Bv 芳香族ジアミン硬化剤からなるエポキシ樹脂
WO2020054601A1 (fr) * 2018-09-12 2020-03-19 日本化薬株式会社 Résine de maléimide, composition de résine durcissable, et produit durci de celle-ci

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JP5215909B2 (ja) 2009-02-27 2013-06-19 富士フイルム株式会社 ラビング用布材及びそれを用いたラビング処理方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62155242A (ja) * 1985-12-27 1987-07-10 Mitsui Petrochem Ind Ltd ビス（ｐ−アミノクミル）ベンゼン類の製造方法
JPS62155241A (ja) * 1985-12-27 1987-07-10 Mitsui Petrochem Ind Ltd ビス（ｐ−アミノクミル）ベンゼン類の製造方法
JPS62260819A (ja) * 1986-01-22 1987-11-13 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 熱硬化性組成物
JPH01215822A (ja) * 1987-12-31 1989-08-29 Shell Internatl Res Maatschappij Bv 芳香族ジアミン硬化剤からなるエポキシ樹脂
WO2020054601A1 (fr) * 2018-09-12 2020-03-19 日本化薬株式会社 Résine de maléimide, composition de résine durcissable, et produit durci de celle-ci

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