WO2021246339A1 - エポキシ樹脂組成物及びその硬化物 - Google Patents

エポキシ樹脂組成物及びその硬化物 Download PDF

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Publication number
WO2021246339A1
WO2021246339A1 PCT/JP2021/020524 JP2021020524W WO2021246339A1 WO 2021246339 A1 WO2021246339 A1 WO 2021246339A1 JP 2021020524 W JP2021020524 W JP 2021020524W WO 2021246339 A1 WO2021246339 A1 WO 2021246339A1
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epoxy resin
group
resin composition
resin
parts
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PCT/JP2021/020524
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English (en)
French (fr)
Japanese (ja)
Inventor
正浩 宗
一男 石原
起煥 柳
▲清▼來 林
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Nippon Steel Chemical and Materials Co Ltd
Kukdo Chemical Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
Kukdo Chemical Co Ltd
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Application filed by Nippon Steel Chemical and Materials Co Ltd, Kukdo Chemical Co Ltd filed Critical Nippon Steel Chemical and Materials Co Ltd
Priority to KR1020227043606A priority Critical patent/KR102847516B1/ko
Priority to JP2022528808A priority patent/JP7773464B2/ja
Priority to CN202180039564.4A priority patent/CN115667352A/zh
Priority to US18/007,746 priority patent/US20230227601A1/en
Publication of WO2021246339A1 publication Critical patent/WO2021246339A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • 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
    • C08G59/3218—Carbocyclic compounds
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics

Definitions

  • the present invention relates to an epoxy resin composition, a cured epoxy resin, a prepreg, a laminated board, and a printed wiring board, which are excellent in low dielectric property and high adhesiveness.
  • Epoxy resin is widely used in paints, civil engineering adhesion, casting, electrical and electronic materials, film materials, etc. because it has excellent adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity. In particular, it is widely used in printed wiring board applications, which are one of the electrical and electronic materials, by imparting flame retardancy to epoxy resin.
  • dicyclopentadienephenol resin having an aliphatic skeleton introduced has been used to reduce the dielectric constant for laminated board applications, but it is effective in improving dielectric loss tangent. It was poor and unsatisfactory in terms of adhesion.
  • Patent Document 2 As a resin for obtaining a low dielectric loss tangent, as shown in Patent Document 2 below, an aromatic-modified epoxy resin or the like having an aromatic skeleton introduced has been used. However, there has been a demand for the development of a resin having a low dielectric loss tangent and high adhesive strength.
  • the epoxy resins disclosed in any of the documents do not sufficiently satisfy the required performance based on the recent high functionality, and are insufficient to ensure low dielectric properties and adhesiveness. ..
  • Patent Document 3 discloses a 2,6-disubstituted phenol / dicyclopentadiene type resin, but does not disclose a resin in which a plurality of dicyclopentadiene is substituted in a phenol ring.
  • the problem to be solved by the present invention is to provide an epoxy resin composition that exhibits excellent dielectric loss tangent and further provides a cured product having excellent copper foil peeling strength and interlayer adhesion strength for printed wiring board applications. be.
  • the present inventors have epoxidized a phenol resin obtained by reacting 2,6-di-substituted phenols with a specific ratio of dicyclopentadiene. We have found that when the resin is cured with a curing agent, the obtained cured product has excellent low dielectric properties and adhesiveness, and completed the present invention.
  • the present invention is an epoxy resin composition containing an epoxy resin and a curing agent, and the epoxy resin is characterized in that a part or all of the epoxy resin is an epoxy resin represented by the following general formula (1). It is a composition.
  • R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms
  • R 2 independently represents a hydrogen atom or a dicyclopentenyl group, and at least one is a dicyclopentenyl group.
  • m indicates the number of repetitions, and the average value thereof is a number from 0 to 5.
  • the epoxy equivalent of the epoxy resin is 244 to 3700 g / eq. Is preferable.
  • the curing agent is preferably at least one of phenolic resins, acid anhydrides, amines, cyanate esters, active esters, hydrazides, acidic polyesters, and aromatic cyanates.
  • the present invention is a cured product obtained by curing the above epoxy resin composition. Further, the present invention is a prepreg, a laminated board, or a printed wiring board using the above epoxy resin composition.
  • the epoxy resin composition of the present invention exhibits excellent dielectric loss tangent in the cured product, and further provides an epoxy resin composition having excellent copper foil peeling strength and interlayer adhesion strength for printed wiring board applications. In particular, it can be suitably used for mobile applications and server applications where low dielectric loss tangent is strongly required.
  • 6 is a GPC chart of the multivalent hydroxy compound obtained in Synthesis Example 1.
  • 6 is an IR chart of the multivalent hydroxy compound obtained in Synthesis Example 1.
  • 6 is a GPC chart of the epoxy resin obtained in Synthesis Example 4.
  • the epoxy resin used in the epoxy resin composition of the present invention is represented by the above general formula (1).
  • R 1 represents a hydrocarbon group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t-butyl group or a hexyl group.
  • Cyclohexyl group, methylcyclohexyl group and the like but are not limited thereto.
  • the aryl group having 6 to 8 carbon atoms include, but are not limited to, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group and the like.
  • the aralkyl group having 7 to 8 carbon atoms include, but are not limited to, a benzyl group and an ⁇ -methylbenzyl group. From the viewpoint of easy availability and reactivity when prepared as a cured product, a phenyl group or a methyl group is preferable, and a methyl group is more preferable.
  • R 2 independently represents a hydrogen atom or a dicyclopentenyl group, and at least one R 2 in the molecule is a dicyclopentenyl group.
  • the dicyclopentenyl group is a group derived from dicyclopentadiene and is represented by the following formula (1a) or formula (1b). Due to the presence of this group, the cured product of the epoxy resin composition of the present invention can have a low dielectric constant and a dielectric loss tangent.
  • m is the number of repetitions, indicating a number of 0 or more, and the average value (number average) thereof is 0 to 5, preferably 0.5 to 3, more preferably 0.5 to 2, and 0.6 to 2. 1.8 is more preferred.
  • a normal epoxy resin is a mixture of components having different m, but in such a case, R 2 may have at least one R 2 in one molecule as a dicyclopentenyl group on average. At that time, a reaction product in which all of R 2 is a hydrogen atom may be mixed.
  • the epoxy resin represented by the general formula (1) can be obtained, for example, by reacting the polyvalent hydroxy compound of the following general formula (2) (hereinafter, also referred to as a phenol resin) with epichlorohydrin such as epichlorohydrin. This reaction is carried out according to a conventionally known method.
  • R 1 and R 2 agree with the definition of the above formula (1).
  • n is the number of repetitions, indicating a number of 0 or more, and the average value (number average) thereof is 0 to 5, preferably 0.5 to 3, more preferably 0.6 to 2, and 0.6 to 0.6. 1.8 is more preferred.
  • the polyvalent hydroxy compound has a hydroxyl group equivalent of preferably 230 or more, more preferably 240 or more, and a softening point of preferably 120 ° C. or lower, more preferably 110 ° C. or lower.
  • the molecular weight of the multivalent hydroxy compound is preferably in the range of 400 to 1000 in weight average molecular weight (Mw) and 350 to 800 in number average molecular weight (Mn).
  • the polyvalent hydroxy compound can be obtained by reacting 2,6-di-substituted phenols with dicyclopentadiene in the presence of Lewis acid such as boron trifluoride / ether catalyst.
  • 2,6-di-substituted phenols examples include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, and 2,6-di (n-butyl).
  • 2,6-bis ( ⁇ -methylbenzyl) phenol examples thereof include phenol, 2,6-bis ( ⁇ -methylbenzyl) phenol, 2-ethyl-6-methylphenol, 2-allyl-6-methylphenol, 2-tolyl-6-phenylphenol, etc., but they are easily available.
  • 2,6-diphenylphenol and 2,6-dimethylphenol are preferable, and 2,6-dimethylphenol is particularly preferable, from the viewpoint of sex and reactivity when made into a cured product.
  • the catalyst used for the above reaction is Lewis acid, specifically boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride and the like.
  • boron trifluoride / ether complex is preferable because of its ease of handling.
  • the amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of dicyclopentadiene.
  • dicyclopentadiene is added to the 2,6-di substituted phenol. It is a method of reacting at a predetermined ratio, and dicyclopentadiene may be reacted intermittently in multiple steps. In a typical reaction, the ratio is 0.1-0.25-fold mol of dicyclopentadiene relative to 2,6-di-substituted phenol, whereas in the present invention it is 0.28-2-fold mol.
  • the ratio of dicyclopentadiene to 2,6-disubstituted phenol is preferably 0.28 to 1-fold, preferably 0.3 to 0.5-fold. More preferred.
  • dicyclopentadiene is added intermittently in multiple stages for reaction, 0.8 to 2-fold mol is preferable, and 0.9 to 1.7-fold mol is more preferable.
  • the amount of dicyclopentadiene used at each stage is preferably 0.28 to 1 times the molar amount.
  • a mass spectrometry method is used as a method for confirming that the dicyclopentenyl group represented by the formula (1a) or the formula (1b) is introduced into the polyvalent hydroxy compound represented by the general formula (2).
  • FT-IR measurement can be used.
  • an electrospray mass spectrometry method ESI-MS
  • FD-MS field decomposition method
  • the substituent represented by the formula (1a) or the formula (1b) has been introduced by subjecting the sample obtained by separating the components having different numbers of nuclei by mass spectrometry to GPC or the like.
  • FT-IR measurement method When the FT-IR measurement method is used, a sample dissolved in an organic solvent such as THF is applied onto the KRS-5 cell, and the cell with a sample thin film obtained by drying the organic solvent is measured by FT-IR. Only when the peak derived from the C—O stretching vibration in the phenol nucleus appears near 1210 cm -1 and the formula (1a) or the formula (1b) is introduced, the CH stretching vibration of the olefin moiety of the dicyclopentadiene skeleton is introduced. A peak derived from 3040 cm- 1 appears.
  • the amount of the formula (1a) or the formula (1b) introduced can be quantified by the ratio (A 3040 / A 1210 ) of the peaks (A 1210) in the vicinity. It has been confirmed that the larger the ratio, the better the physical property value, and the preferable ratio (A 3040 / A 1210 ) for satisfying the target physical property is 0.05 or more, more preferably 0.10 or more.
  • the reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 180 ° C, and even more preferably 120 to 160 ° C.
  • the reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, still more preferably 4 to 8 hours.
  • Solvents such as aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and ethers such as ethylene glycol dimethyl ether and diethylene glucol dimethyl ether, if necessary, during the reaction. May be used.
  • the epoxy resin represented by the general formula (1) can be obtained, for example, by epoxidizing the phenol resin.
  • an alkali metal hydroxide such as sodium hydroxide is added as a solid or concentrated aqueous solution to a mixture of a phenol resin and epihalohydrin having an excess amount with respect to the hydroxyl group of the phenol resin, and 30 to 120.
  • the reaction is carried out at a reaction temperature of ° C. for 0.5 to 10 hours, or a quaternary ammonium salt such as tetraethylammonium chloride is added as a catalyst to the phenol resin and an excess amount of epihalohydrin, and the temperature is 1 to 5 at 50 to 150 ° C.
  • the amount of epihalohydrin used is 1 to 20 times the molar amount of the hydroxyl group of the phenol resin, preferably 2 to 8 times the molar amount.
  • the amount of alkali metal hydroxide used is 0.85 to 1.15 times the molar amount of the hydroxyl group of the phenol resin.
  • the epoxy resin obtained by these reactions contains unreacted epihalohydrin and alkali metal halide
  • the unreacted epihalohydrin is evaporated and removed from the reaction mixture, and the alkali metal halide is further extracted with water.
  • the desired epoxy resin can be obtained by removing the epoxy resin by a method such as filtration.
  • the epoxy equivalent (g / eq.) Of the epoxy resin is preferably 250 or more, more preferably 300 or more, still more preferably 350 or more.
  • the epoxy equivalent is preferably 300 or more in order to prevent crystals of dicyandiamide from precipitating on the prepreg.
  • the epoxy resin has a softening point of preferably 100 ° C. or lower, more preferably 90 ° C. or lower.
  • the total chlorine content is preferably 1000 ppm or less, more preferably 700 ppm or less.
  • the molecular weight distribution of the epoxy resin can be changed by changing the charging ratio of the phenol resin and epihalohydrin during the epoxidation reaction, and the molecular weight is increased so that the amount of epihalohydrin used is closer to equimolar to the hydroxyl group of the phenol resin.
  • the distribution becomes smaller, and the closer it is to 20 mol times, the lower the molecular weight distribution.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the epoxy resin composition of the present invention can be obtained.
  • the epoxy resin composition of the present invention contains the epoxy resin represented by the above general formula (1) and a curing agent as essential components.
  • the epoxy resin represented by the above general formula (1)
  • a curing agent as essential components.
  • one type or two or more types of other epoxy resins may be used in combination, if necessary.
  • the other epoxy resin is preferably 70% by mass or less, more preferably 50% by mass or less of the total epoxy resin. If there are too many other epoxy resins, the dielectric properties of the epoxy resin composition may deteriorate.
  • epoxy resins all ordinary epoxy resins having two or more epoxy groups in the molecule can be used.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol AF type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, stilben type epoxy resin, bisphenol fluorene type epoxy.
  • Glycidylamine type epoxy resin such as amine and aminophenol type epoxy resin, alicyclic epoxy resin such as celloxide 2021P (manufactured by Daicel Co., Ltd.), phosphorus-containing epoxy resin, bromine-containing epoxy resin, urethane-modified epoxy resin, oxazolidone ring-containing epoxy Examples thereof include, but are not limited to, resins.
  • an epoxy resin an aromatic-modified phenol novolac type epoxy resin, a cresol novolac type epoxy resin, an ⁇ -naphthol aralkyl type epoxy resin, a dicyclopentadiene type epoxy resin, a phosphorus-containing epoxy resin, and an oxazolidone ring-containing epoxy resin. ..
  • R 3 independently represents a hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and the like. It is an alkyl group such as a cyclohexyl group, and may be the same or different from each other.
  • X represents a divalent group, for example, an alkylene group such as a methylene group, an ethylene group, an isopropyredene group, an isobutylene group, a hexafluoroisopropyridene group, -CO-, -O-, -S-, -SO 2- , -SS-, or an aralkylene group represented by the formula (4) is shown.
  • R 4 represents one or more number of hydrogen atoms or carbon independently a hydrocarbon group, for example a methyl group, may be different even in the same to each other.
  • Ar is a benzene ring or a naphthalene ring, and these benzene rings or naphthalene rings have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, and 7 to 7 carbon atoms. It may have 12 aralkyl groups, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent.
  • various phenol resins, acid anhydrides, amines, cyanate esters, active esters, hydrazides, acidic polyesters, aromatic cyanates and the like which are usually used are used as necessary.
  • One type or two or more types may be used in combination.
  • the molar ratio of the active hydrogen group of the curing agent is preferably 0.2 to 1.5 mol, preferably 0.3 to 1.4 mol, with respect to 1 mol of the epoxy group of the total epoxy resin. Is more preferable, 0.5 to 1.3 mol is further preferable, and 0.8 to 1.2 mol is particularly preferable. If it is out of this range, curing may be incomplete and good cured physical properties may not be obtained.
  • an active hydrogen group is blended in approximately equal molar amounts with respect to the epoxy group.
  • an acid anhydride-based curing agent When an acid anhydride-based curing agent is used, 0.5 to 1.2 mol, preferably 0.6 to 1.0 mol, of the acid anhydride group is blended with respect to 1 mol of the epoxy group.
  • the phenol resin of the present invention When the phenol resin of the present invention is used alone as a curing agent, it is desirable to use it in the range of 0.9 to 1.1 mol with respect to 1 mol of the epoxy resin.
  • the active hydrogen group referred to in the present invention includes a functional group having an active hydrogen reactive with an epoxy group (a functional group having a latent active hydrogen that produces active hydrogen by hydrolysis or the like, and a functional group exhibiting an equivalent curing action. .), Specific examples thereof include an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group and the like. Regarding the active hydrogen group, 1 mol of the carboxyl group and the phenolic hydroxyl group are calculated as 1 mol, and the amino group (NH 2 ) is calculated as 2 mol. If the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement.
  • the active hydrogen equivalent of the curing agent used is measured by reacting a monoepoxy resin such as phenylglycidyl ether having a known epoxy equivalent with a curing agent having an unknown active hydrogen equivalent and measuring the amount of the monoepoxy resin consumed. Can be asked.
  • a monoepoxy resin such as phenylglycidyl ether having a known epoxy equivalent
  • a curing agent having an unknown active hydrogen equivalent can be asked.
  • Bisphenols such as bisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, tetrabromobisphenol A, dihydroxydiphenylsulfide, 4,4'-thiobis (3-methyl-6-t-butylphenol), catechol, resorcin, methyl Dihydroxybenzenes such as resorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-t-butylhydroquinone, di-t-butylhydroquinone, and hydroxynaphthalene such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene.
  • examples thereof include a phenol compound called a so-called novolak phenol resin, a polybutadiene-modified phenol resin, and a phenol resin having a spiro ring. From the viewpoint of easy availability, phenol novolac resin, dicyclopentadiene type phenol resin, trishydroxyphenylmethane type novolak resin, aromatic-modified phenol novolak resin and the like are preferable.
  • Phenol novolak resin can be obtained from phenols and a cross-linking agent.
  • the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, 1-naphthol, 2-naphthol and the like, and other phenol resin-based curing agents.
  • the listed bisphenols can be mentioned.
  • Aldehydes as cross-linking agents include formaldehyde, acetaldehyde, propyl aldehyde, butyl aldehyde, barrel aldehyde, capron aldehyde, benz aldehyde, chlor aldehyde, brom aldehyde, glioxal, malon aldehyde, succin aldehyde, glutal aldehyde, adipine aldehyde, and pimerin. Examples thereof include aldehyde, sebacin aldehyde, achlorine, croton aldehyde, salicyl aldehyde, phthal aldehyde, hydroxybenz aldehyde and the like.
  • the biphenyl-based cross-linking agent include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, and bis (chloromethyl) biphenyl.
  • acid anhydride-based curing agent examples include maleic anhydride, methyltetrahydrophthalic acid anhydride, phthalic acid anhydride, 4-methylhexahydrophthalic acid anhydride, and methylbicyclo [2.2.1] heptane-2.
  • 3-Dicarboxylic acid anhydride Bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, 1,2,3,6-tetrahydrohydrochloride phthalic acid, pyromellitic anhydride, phthalic acid anhydride, anhydrous Examples thereof include trimellitic acid, methylnadic acid, a copolymer of a styrene monomer and maleic anhydride, and a copolymer of indens and maleic anhydride.
  • amine-based curing agent examples include diethylenetriamine, triethylenetetramine, metaxylenedamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulphon, diaminodiphenylether, benzyldimethylamine, and 2,4,6-tris (dimethylaminomethyl).
  • aromatic amines such as phenol, polyether amines, biguanide compounds, dicyandiamide and anicidine, and amine compounds such as polyamide amines which are condensates of acids such as dimer acid and polyamines.
  • the cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanate groups (cyanic acid ester groups) in one molecule.
  • novolak-type cyanate ester-based curing agents such as phenol novolac type and alkylphenol novolak type, naphthol aralkyl type cyanate ester-based curing agent, biphenylalkyl type cyanate ester-based curing agent, dicyclopentadiene type cyanate ester-based curing agent, bisphenol A type.
  • cyanate ester-based curing agent examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), bis (3-methyl-4-cyanate phenyl) methane, and bis (3).
  • the active ester-based curing agent is not particularly limited, but generally contains an ester group having high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used.
  • the active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
  • an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
  • the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
  • phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglucin, benzenetriol , Dicyclopentadienyldiphenol, phenol novolac, polyvalent hydroxy compound of the above general formula (2) and the like.
  • One kind or two or more kinds of active ester-based curing agents can be used.
  • the active ester-based curing agent include an active ester-based curing agent containing a dicyclopentadienyldiphenol structure, an active ester-based curing agent containing a naphthalene structure, and an active ester-based curing agent which is an acetylated product of phenol novolac.
  • An active ester-based curing agent which is a benzoylated product of phenol novolac is preferable, and among them, a dicyclopentadienyldiphenol structure such as a polyvalent hydroxy compound of the above general formula (2) is excellent in that it is excellent in improving peel strength.
  • An active ester-based curing agent containing the above is more preferable.
  • curing agents include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, and 2-un.
  • phosphine compounds such as triphenylphosphine
  • phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, and 2-un.
  • Imidazoles such as decylimidazole and 1-cyanoethyl-2-methylimidazole, imidazole salts which are salts of imidazoles and trimellitic acid, isocyanuric acid, or boron and the like, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds, Examples thereof include salts of diazabicyclo compounds and phenols, phenol novolac resins and the like, complex compounds of boron trifluoride with amines and ether compounds, aromatic phosphoniums, iodonium salts and the like.
  • a curing accelerator can be used for the epoxy resin composition if necessary.
  • curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8. -Primary amines such as diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphin triphenylborane, and metal compounds such as tin octylate. Will be.
  • the amount used is preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition of the present invention.
  • An organic solvent or a reactive diluent can be used for adjusting the viscosity of the epoxy resin composition.
  • organic solvent examples include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether.
  • amides such as N, N-dimethylformamide and N, N-dimethylacetamide
  • ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propy
  • Alcohols such as pine oil, acetates such as butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate, and benzoic acid.
  • Aromas such as benzoic acid esters such as methyl and ethyl benzoate, cellosolves such as methyl cellosolve, cellosolve and butyl cellosolve, carbitols such as methylcarbitol, carbitol and butylcarbitol, and fragrances such as benzene, toluene and xylene.
  • Group hydrocarbons, dimethylsulfoxide, acetonitrile, N-methylpyrrolidone and the like can be mentioned, but the present invention is not limited thereto.
  • Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and trill glycidyl ether, and monofunctional glycidyl esters such as neodecanoic acid glycidyl ester. Etc., but are not limited to these.
  • organic solvents or reactive diluents alone or in a mixture of a plurality of types in an amount of 90% by mass or less as the non-volatile content, and the appropriate type and amount to be used are appropriately selected depending on the intended use.
  • a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, or 1-methoxy-2-propanol, is preferable, and the amount used is preferably 40 to 80% by mass in terms of non-volatile content.
  • ketones, acetic acid esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the amount used is a non-volatile content. 30 to 60% by mass is preferable.
  • the epoxy resin composition may contain other thermosetting resins and thermoplastic resins as long as the characteristics are not impaired.
  • phenol resin benzoxazine resin, bismaleimide resin, bismaleimide triazine resin, acrylic resin, petroleum resin, inden resin, kumaron inden resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, Containing reactive functional groups such as polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinylformal resin, polysiloxane compound, hydroxyl group-containing polybutadiene, etc.
  • alkylene resins examples include, but are not limited to, alkylene resins.
  • Various known flame retardants can be used in the epoxy resin composition for the purpose of improving the flame retardancy of the obtained cured product.
  • the flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, organic metal salt-based flame retardants, and the like. From the viewpoint of the environment, halogen-free flame retardants are preferable, and phosphorus-based flame retardants are particularly preferable. These flame retardants may be used alone or in combination of two or more.
  • an inorganic phosphorus compound or an organic phosphorus compound can be used as the phosphorus flame retardant.
  • the inorganic phosphorus-based compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. Be done.
  • organophosphorus compounds examples include aliphatic phosphoric acid esters and phosphoric acid ester compounds, for example, condensed phosphoric acid esters such as PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), phosphazene, phosphonic acid compounds, and phosphinic acid compounds. , Phosphine oxide compounds, phosphoran compounds, general-purpose organophosphorus compounds such as organonitrous-containing phosphorus compounds, metal salts of phosphinic acid, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
  • Examples thereof include cyclic organic phosphorus compounds such as faphenanthren-10-oxide, phosphorus-containing epoxy resins and phosphorus-containing curing agents which are derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.
  • the amount of the flame retardant to be blended is appropriately selected depending on the type of the phosphorus-based flame retardant, the components of the epoxy resin composition, and the desired degree of flame retardancy.
  • the phosphorus content in the organic component (excluding the organic solvent) in the epoxy resin composition is preferably 0.2 to 4% by mass, more preferably 0.4 to 3.5% by mass, and further. It is preferably 0.6 to 3% by mass. If the phosphorus content is low, it may be difficult to secure flame retardancy, and if it is too high, the heat resistance may be adversely affected.
  • a flame retardant aid such as magnesium hydroxide may be used in combination.
  • a filler can be used for the epoxy resin composition as needed. Specifically, molten silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, Borone nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine particle rubber, silicone rubber, thermoplastic elastomer, carbon black, pigment, etc. Can be mentioned. Generally, the reason for using a filler is the effect of improving impact resistance.
  • a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide
  • it acts as a flame retardant aid and has an effect of improving flame retardancy.
  • the blending amount of these fillers is preferably 1 to 150% by mass, more preferably 10 to 70% by mass, based on the entire epoxy resin composition. If the blending amount is large, the adhesiveness required for laminated board applications may decrease, and the cured product may become brittle, making it impossible to obtain sufficient mechanical properties. Further, if the blending amount is small, there is a possibility that the blending effect of the filler may not be obtained, such as improvement of the impact resistance of the cured product.
  • the epoxy resin composition is a plate-shaped substrate or the like
  • a fibrous one is mentioned as a preferable filler in terms of its dimensional stability, bending strength and the like. More preferably, a glass fiber substrate in which glass fibers are knitted in a mesh shape can be mentioned.
  • the epoxy resin composition further contains various additives such as a silane coupling agent, an antioxidant, a mold release agent, a defoaming agent, an emulsifier, a rocking denaturing agent, a smoothing agent, a flame retardant, and a pigment, if necessary. be able to.
  • the blending amount of these additives is preferably in the range of 0.01 to 20% by mass with respect to the epoxy resin composition.
  • the epoxy resin composition can be impregnated into a fibrous base material to prepare a prepreg used in a printed wiring board or the like.
  • a fibrous base material inorganic fibers such as glass, woven fabrics or non-woven fabrics of organic fibers such as polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin such as polyester resin can be used, but are limited thereto. It's not something.
  • the method for producing the prepreg from the epoxy resin composition is not particularly limited. For example, the epoxy resin composition is dipped in a resin varnish prepared by adjusting the viscosity with an organic solvent, impregnated, and then heated and dried to make a resin.
  • the amount of resin in the prepreg is preferably 30 to 80% by mass of the resin content.
  • a method for curing a laminated board generally used when manufacturing a printed wiring board can be used, but the method is not limited thereto.
  • a laminated board using a prepreg one or a plurality of prepregs are laminated, metal foils are arranged on one side or both sides to form a laminate, and the laminate is heated and pressed to be integrated.
  • the metal foil a single metal leaf such as copper, aluminum, brass, nickel or the like, an alloy, or a composite metal leaf can be used. Then, the prepared laminate is pressurized and heated to cure the prepreg, and a laminate can be obtained.
  • the heating temperature is 160 to 220 ° C.
  • the pressurizing pressure is 50 to 500 N / cm 2
  • the heating and pressurizing time is 40 to 240 minutes, and the desired cured product can be obtained. If the heating temperature is low, the curing reaction does not proceed sufficiently, and if it is high, decomposition of the epoxy resin composition may start. In addition, if the pressurizing pressure is low, air bubbles may remain inside the obtained laminated board and the electrical characteristics may deteriorate, and if it is high, the resin will flow before curing, and a cured product of the desired thickness can be obtained. There is a risk that it will not be possible. Further, if the heating and pressurizing time is short, the curing reaction may not proceed sufficiently, and if it is long, the epoxy resin composition in the prepreg may be thermally decomposed, which is not preferable.
  • the epoxy resin composition can be cured in the same manner as the known epoxy resin composition to obtain a cured epoxy resin composition.
  • a method for obtaining a cured product the same method as that of a known epoxy resin composition can be taken, such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, resin sheet, resin, etc.
  • a method such as forming a laminated plate by laminating in the form of a copper foil, a prepreg, or the like and curing by heating and pressure is preferably used.
  • the curing temperature at that time is usually 100 to 300 ° C., and the curing time is usually about 1 hour to 5 hours.
  • the cured epoxy resin of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film, or the like.
  • ⁇ Hydroxy group equivalent The measurement was performed in accordance with the JIS K 0070 standard, and the unit was expressed as "g / eq.”. Unless otherwise specified, the hydroxyl group equivalent of the phenol resin means the phenolic hydroxyl group equivalent.
  • ⁇ Flame retardance It was evaluated by the vertical method according to UL94. The evaluation was described by V-0, V-1, and V-2.
  • Tg -Glass transition temperature
  • Relative permittivity and dielectric loss tangent It was evaluated by obtaining the relative permittivity and the dielectric loss tangent at a frequency of 1 GHz by the capacitive method using a material analyzer (manufactured by Agilent Technologies) according to IPC-TM-650 2.5.5.9.
  • 0.1 g of the sample was dissolved in 10 mL of THF, and 50 ⁇ L of the sample filtered through a microfilter was used.
  • GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation was used.
  • ⁇ IR A Fourier transform infrared spectrophotometer (manufactured by PerkinElmer Precision, Spectrum One FT-IR Spectrometer 1760X) was used, KRS-5 was used for the cell, and a sample dissolved in THF was applied onto the cell and dried. After that, the absorbance with a wave number of 650 to 4000 cm -1 was measured.
  • ⁇ ESI-MS Mass spectrometry was performed by using a mass spectrometer (LCMS-2020, manufactured by Shimadzu Corporation), using acetonitrile and water as mobile phases, and measuring a sample dissolved in acetonitrile.
  • E1 Epoxy resin obtained in Synthesis Example 1
  • E2 Epoxy resin obtained in Synthesis Example 2
  • E3 Epoxy resin obtained in Synthesis Example 3
  • E4 Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000, epoxy) Equivalent 274, softening point 60 ° C)
  • E5 Triphenol methane type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EPPN-501H, epoxy equivalent 166)
  • E6 Phosphorus-containing epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., FX-1225, epoxy equivalent 317, phosphorus content)
  • E7 Naphthalene type epoxy resin (manufactured by Nittetsu Chemical & Materials Co., Ltd., ESN-475V, epoxy equivalent 325)
  • E8 Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX-4000H
  • P1 Phenol novolak resin (manufactured by Aica SDK Phenol Co., Ltd., BRG-557, hydroxyl group equivalent 105, softening point 85 ° C)
  • P2 Dicyclopentadiene type phenol resin (manufactured by Gun Ei Chemical Industry Co., Ltd., GDP-6140, hydroxyl group equivalent 196, softening point 130 ° C)
  • P3 Trishydroxyphenylmethane type novolak resin (manufactured by Gun Ei Chemical Industry Co., Ltd., Reditop TPM-100, hydroxyl group equivalent 98, softening point 108 ° C)
  • P4 Biphenyl aralkyl type phenol resin (manufactured by Meiwa Kasei Co., Ltd., MEH-7851, hydroxyl group equivalent 223, softening point 75 ° C)
  • P5 Naphthol type curing agent (manufactured by Nittetsu
  • B1 BPF type benzoxazine resin (manufactured by Shikoku Chemicals Corporation, FA type benzoxazine resin)
  • C1 2E4MZ: 2-Ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Corporation, Curesol 2E4MZ)
  • C2 Triphenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd., Hokuko TPP)
  • C3 2-Phenylimidazole (Curesol 2PZ, manufactured by Shikoku Chemicals Corporation)
  • C4 4-Dimethylaminopyridine (manufactured by Kishida Chemical Co., Ltd.)
  • [filler] F1 Hollow glass filler (manufactured by 3M Japan Ltd., Glass Bubbles iM30K, average particle size (d50) 16 ⁇ m)
  • Synthesis example 1 140 parts of 2,6-xylenol, 9.3 parts of 47% BF 3 ether complex (to dicyclopentadiene to be added first) to a reactor equipped with a stirrer, thermometer, nitrogen blowing tube, dropping funnel, and condenser. 0.1 times the molar amount) was charged and heated to 110 ° C. with stirring. While maintaining the same temperature, 86.6 parts of dicyclopentadiene (0.57 times mol with respect to 2,6-xylenol) was added dropwise over 1 hour. After further reacting at a temperature of 110 ° C.
  • the MIBK was evaporated and removed by heating to 160 ° C. under a reduced pressure of 5 mmHg to obtain 274 parts of a reddish brown polyvalent hydroxy compound.
  • the resin had a hydroxyl group equivalent of 299 and a softening point of 97 ° C., and had an absorption ratio (A 3040 / A 1210 ) of 0.17.
  • M- 253, 375, 507, 629 was confirmed.
  • the GPC of the obtained multivalent hydroxy compound is shown in FIG. 1, and the FT-IR is shown in FIG. 2, respectively.
  • c shows the peak derived from the CH expansion and contraction vibration of the olefin moiety of the dicyclopentadiene skeleton, and d shows the absorption by the CH expansion and contraction vibration in the phenol nucleus.
  • the resin had an epoxy equivalent of 358, a total chlorine content of 520 ppm, and a softening point of 80 ° C.
  • Synthesis example 2 In the same reaction apparatus as in Synthesis Example 1, 140 parts of 2,6-xylenol and 9.3 parts of 47% BF 3 ether complex (0.1 times by mole with respect to the dicyclopentadiene added first) were charged and stirred. While warming to 110 ° C. While maintaining the same temperature, 86.6 parts of dicyclopentadiene (0.57 times mol with respect to 2,6-xylenol) was added dropwise over 1 hour. After further reacting at a temperature of 110 ° C. for 3 hours, 90.6 parts of dicyclopentadiene (0.60 times mol with respect to 2,6-xylenol) was added dropwise in 1 hour while maintaining the same temperature. The reaction was further carried out at 120 ° C.
  • the resin had a hydroxyl group equivalent of 341 and a softening point of 104 ° C., and had an absorption ratio (A 3040 / A 1210 ) of 0.27.
  • M- 253, 375, 507, 629 was confirmed.
  • Mw 830
  • Mn 530
  • n 0 body content is 5.9 area%
  • n 1 body content is 60.1%
  • n 2 or more body content is 34.0%. there were.
  • 200 parts of this polyvalent hydroxy compound, 271 parts of epichlorohydrin and 81 parts of diethylene glycol dimethyl ether were added and heated to 65 ° C.
  • the resin solution was washed with water until the washing liquid became neutral, and then filtered.
  • the MIBK was distilled off by heating to 180 ° C. under a reduced pressure of 5 mmHg to obtain 221 parts of a reddish brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin (E2).
  • the resin had an epoxy equivalent of 421, a total chlorine content of 530 ppm, and a softening point of 84 ° C.
  • Synthesis example 3 In the same reaction apparatus as in Synthesis Example 1, 140 parts of 2,6-xylenol and 9.3 parts of 47% BF 3 ether complex (0.1 times by mole with respect to the dicyclopentadiene added first) were charged and stirred. While warming to 110 ° C. While maintaining the same temperature, 86.6 parts of dicyclopentadiene (0.57 times mol with respect to 2,6-xylenol) was added dropwise over 1 hour. After further reacting at a temperature of 110 ° C. for 3 hours, 56.7 parts of dicyclopentadiene (0.37 times mol with respect to 2,6-xylenol) was added dropwise in 1 hour while maintaining the same temperature. The reaction was further carried out at 120 ° C.
  • the hydroxyl group equivalent was 272, the resin had a softening point of 91 ° C., and the absorption ratio (A 3040 / A 1210 ) was 0.14.
  • M- 253, 375, 507, 629 was confirmed.
  • Mw 680
  • Mn 530
  • n 0 body content is 5.9 area%
  • n 1 body content is 75.1%
  • n 2 or more body content is 19.0%. there were.
  • 200 parts of this polyvalent hydroxy compound, 170 parts of epichlorohydrin and 51 parts of diethylene glycol dimethyl ether were added and heated to 65 ° C.
  • the resin solution was washed with water until the washing liquid became neutral, and then filtered.
  • the MIBK was distilled off by heating to 180 ° C. under a reduced pressure of 5 mmHg to obtain 229 parts of a reddish brown transparent 2,6-xylenol-dicyclopentadiene type epoxy resin (E3).
  • the resin had an epoxy equivalent of 358, a total chlorine content of 570 ppm, and a softening point of 76 ° C.
  • Synthesis example 4 400 parts of phenol and 7.5 parts of 47% BF 3 ether complex were charged in the same reaction apparatus as in Synthesis Example 1 and heated to 70 ° C. with stirring. While maintaining the same temperature, 70.2 parts of dicyclopentadiene was added dropwise over 2 hours. Further, the reaction was carried out at a temperature of 125 to 135 ° C. for 4 hours, and 11.7 parts of calcium hydroxide was added. Further, 35 parts of a 10% oxalic acid aqueous solution was added. Then, it was heated to 160 ° C. and dehydrated, and then heated to 200 ° C. under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw material.
  • Example 1 100 parts of E1 as an epoxy resin, 37 parts of P1 as a curing agent, and 0.22 parts of C1 as a curing accelerator are blended and dissolved in a mixed solvent prepared with MEK, propylene glycol monomethyl ether, and N, N-dimethylformamide.
  • the epoxy resin composition varnish was obtained.
  • the obtained epoxy resin composition varnish was impregnated into a glass cloth (WEA 7628 XS13, 0.18 mm thick, manufactured by Nitto Boseki Co., Ltd.). The impregnated glass cloth was dried in a hot air circulation oven at 150 ° C. for 9 minutes to obtain a prepreg.
  • the obtained prepreg was loosened and sieved to make a powdery prepreg powder with a 100 mesh pass.
  • the obtained prepreg powder was placed in a fluororesin mold and vacuum pressed at 2 MPa under the temperature conditions of 130 ° C. ⁇ 15 minutes + 190 ° C. ⁇ 80 minutes to obtain a 50 mm square ⁇ 2 mm thick test piece.
  • Table 1 shows the results of the relative permittivity and dielectric loss tangent of the test piece.
  • Examples 2 to 11 and Comparative Examples 1 to 12 The blending amounts (parts) shown in Tables 1 to 3 were blended, and the same operation as in Example 1 was carried out to obtain a laminated board and a test piece. The amount of the curing accelerator was adjusted so that the varnish gel time could be adjusted to about 300 seconds. The same test as in Example 1 was performed, and the results are shown in Tables 1 to 3.
  • Example 12 and Comparative Examples 13 to 15 The compounding amount (part) in Table 4 was compounded, and the same operation as in Example 1 was carried out to obtain a laminated board and a test piece.
  • Table 4 shows the measurement results of flame retardancy, copper foil peeling strength, interlayer adhesive strength, and Tg of the laminated board, and the measurement results of the relative permittivity and the dielectric loss tangent of the test piece.
  • Example 13 In order to evaluate as a casting resin, 50 parts of E2 and 50 parts of E8 as an epoxy resin, 32 parts of P1 as a curing agent, and 1.0 part of C2 as a curing accelerator are kneaded to obtain a resin composition. rice field. The obtained epoxy resin composition was molded at 175 ° C., and further post-cured at 175 ° C. for 12 hours to obtain a cured product. Table 5 shows the measurement results of the relative permittivity, dielectric loss tangent, and Tg of the cured product.
  • Example 14 to 15 and Comparative Examples 16 to 18 The mixture was blended in the blending amount (part) shown in Table 5, and the same operation as in Example 13 was carried out to obtain a cured product.
  • Table 5 shows the results of the same test as in Example 13.
  • the epoxy resin composition of the present invention can provide a cured resin product which exhibits very good low dielectric properties and also has excellent adhesive strength.
  • the epoxy resin composition of the present invention has excellent dielectric properties, heat resistance, and adhesiveness, and can be used for various purposes such as lamination, molding, and adhesion, and is particularly useful as an electronic material for high-speed communication equipment.

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PCT/JP2021/020524 2020-06-04 2021-05-28 エポキシ樹脂組成物及びその硬化物 Ceased WO2021246339A1 (ja)

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