阅读说明：本技术 环氧树脂组合物 (Epoxy resin composition ) 是由 尾崎充孝 郭思博 于 2019-10-03 设计创作，主要内容包括：本发明的课题在于提供一种不仅耐热性优异且介电特性也优异的环氧树脂组合物。作为解决方法,提供一种环氧树脂组合物,其特征在于,含有(A)特征为由式(1)及/或式(2)及/或式(3)所表示,且重均分子量(Mw)为500以上10,000以下的范围的聚碳酸酯寡聚物,和(B)1分子中具有2个以上环氧基的聚环氧化合物。(The present invention addresses the problem of providing an epoxy resin composition that has excellent dielectric properties in addition to excellent heat resistance. Specifically disclosed is an epoxy resin composition which is characterized by containing (A) a polycarbonate oligomer which is characterized by being represented by formula (1) and/or formula (2) and/or formula (3) and has a weight average molecular weight (Mw) in the range of 500 to 10,000, and (B)1 a polyepoxide compound which has 2 or more epoxy groups in the molecule.)

1. An epoxy resin composition characterized by comprising (A) a polycarbonate oligomer which is characterized by being represented by the following formula (1) and/or formula (2) and/or formula (3) and has a weight average molecular weight Mw in the range of 500 to 10,000, and (B)1 a polyepoxide compound having 2 or more epoxy groups in the molecule,

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

In the formulae (1), (2) and (3), R₁、R₂、R₃And R₄Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, X represents a single bond, an alkylene group having 1 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylene group, an adamantan-1, 3-ylidene group, an adamantan-2-ylidene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or a fluorene-9-ylidene group, and n is an integer of 1 or more, wherein R is an integer of 1 or more₁、R₂、R₃And R₄All represent hydrogen atoms and X is isopropylidene, except where.

2. A cured product obtained by curing the epoxy resin composition according to claim 1.

Technical Field

The present invention relates to an epoxy resin composition having excellent heat resistance and dielectric characteristics.

Background

Epoxy resins are cured with a curing agent to give cured products excellent in mechanical properties, adhesion, water resistance, chemical resistance, heat resistance, electrical insulation, and the like, and thus are used in a wide range of fields such as adhesives, paints, laminates, molding materials, and casting materials.

For example, patent documents 1 and 2 specifically disclose that an epoxy resin foam having excellent flexibility, and heat resistance and improved mechanical properties can be obtained by using a bisphenol a type polycarbonate oligomer as a curing agent, but the performance such as heat resistance is not sufficient at a level required in recent years.

Patent document

Patent document 1: japanese laid-open patent publication No. H01-103633

Patent document 2: japanese patent laid-open publication No. H04-16337

Disclosure of Invention

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an epoxy resin composition having excellent heat resistance and also excellent dielectric properties.

The present inventors have intensively studied to solve the above problems and found that an epoxy resin composition obtained by combining a polycarbonate oligomer characterized by being represented by the following formula (1) and/or formula (2) and/or formula (3) and having a weight average molecular weight (Mw) in the range of 500 to 10,000 as a curing agent with a polyepoxy compound having 2 or more epoxy groups in 1 molecule can improve not only heat resistance but also dielectric characteristics, and thus completed the present invention.

The present invention is as follows.

1. An epoxy resin composition characterized by comprising (A) a polycarbonate oligomer which is characterized by being represented by the following formula (1) and/or formula (2) and/or formula (3) and has a weight average molecular weight (Mw) in the range of 500 to 10,000, and (B)1 a polyepoxide compound having 2 or more epoxy groups in the molecule,

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

In the formulae (1), (2) and (3), R₁、R₂、R₃And R₄Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, X represents a single bond, an alkylene group having 1 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylene group, an adamantan-1, 3-ylidene group, an adamantan-2-ylidene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or a fluorene-9-ylidene group, and n is an integer of 1 or more, wherein R is an integer of 1 or more₁、R₂、R₃And R₄All represent hydrogen atoms and X is isopropylidene, except where.

2. A cured product obtained by curing the epoxy resin composition described in the above item 1.

The epoxy resin composition of the present invention contains a polycarbonate oligomer represented by formula (1) and/or formula (2) and/or formula (3) and having a specific weight average molecular weight as a curing agent, and thus has improved dielectric properties and industrially advantageous effects.

Furthermore, a cured product obtained by curing the epoxy resin composition of the present invention has a high glass transition temperature and excellent heat resistance, and therefore, is suitable as an industrial material requiring heat resistance.

Detailed Description

The epoxy resin composition of the present invention will be described in detail below.

< ingredient (A) >, relating to the present invention

The polycarbonate oligomer as the component (a) in the present invention has a weight average molecular weight (Mw) in the range of 500 to 10,000, and is a compound represented by the following formula (1) and/or formula (2) and/or formula (3).

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

(in the formulae (1), (2) and (3), R₁、R₂、R₃And R₄Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, X represents a single bond, an alkylene group having 1 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylene group, an adamantan-1, 3-ylidene group, an adamantan-2-ylidene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group or a fluorene-9-ylidene group, and n is an integer of 1 or more. Wherein R is₁、R₂、R₃And R₄All represent hydrogen atoms and X is isopropylidene, except where. )

In the above formulae (1) to (3), R₁、R₂、R₃And R₄When any one of them is an alkyl group having 1 to 8 carbon atomsThe alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an isobutyl group. The alkyl group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms, for example, in the range not to impair the effects of the present invention.

In the above formulae (1) to (3), R₁、R₂、R₃And R₄When any one of them is a cycloalkyl group having 5 to 12 carbon atoms, the cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms, and specific examples thereof include cyclohexyl, cyclopentyl, cycloheptyl, and the like. The cycloalkyl group may have a substituent such as a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group, as long as the effects of the present invention are not impaired.

In the above formulae (1) to (3), R is₁、R₂、R₃And R₄When any one of the alkoxy groups is a C1-8 alkoxy group, the alkoxy group is preferably a C1-4 linear or branched alkoxy group, and specifically, examples thereof include a methoxy group and an ethoxy group. The alkoxy group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms within a range not to impair the effects of the present invention.

Further, in the above formulae (1) to (3), R₁、R₂、R₃And R₄When any one of the aromatic hydrocarbon groups is an aromatic hydrocarbon group having 6 to 12 carbon atoms, specific examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. The aromatic hydrocarbon group may be substituted by, for example, an alkyl group having 1 to 4 carbon atoms and/or an alkoxy group having 1 to 4 carbon atoms by about 1 to 3 groups within a range not to impair the effects of the present invention.

In the formulae (1) to (3), when X is an alkylene group having 1 to 15 carbon atoms, the alkylene group is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, more preferably a linear or branched alkylene group having 1 to 4 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. The alkylene group may have a substituent such as an aromatic hydrocarbon group or an alkoxy group, and examples thereof include a phenylmethylene group and a diphenylmethylene group, as long as the effects of the present invention are not impaired.

In the above formulae (1) to (3), when X is a cycloalkylene group having 5 to 15 carbon atoms, the cycloalkylene group is preferably a cycloalkylene group having 5 to 7 carbon atoms, and specific examples thereof include a 1, 3-cyclopentylene group, a 1, 4-cyclohexylene group, and a 1, 3-cyclohexylene group. The alkylene group may be substituted with, for example, an alkyl group having 1 to 4 carbon atoms by about 1 to 3 groups within a range not to impair the effects of the present invention.

In the above formulae (1) to (3), when X is an alkylidene group having 2 to 15 carbon atoms, a preferred alkylidene group is a linear or branched alkylidene group having 2 to 15 carbon atoms, and specific examples thereof include ethylidene, prop-1-ene, isopropylidene, but-1-ene, but-2-ene, 2-methylpropan-1-ene, pent-2-ene, 3-methylbut-1-ene, hex-2-ene, hept-4-ene, 2-ethylhex-1-ene, and non-2-ene.

The alkylidene group may have a substituent such as an aromatic hydrocarbon group or an alkoxy group as long as the effects of the present invention are not impaired.

In the above formulae (1) to (3), when X is a cycloalkylidene group having 5 to 15 carbon atoms, specific examples of the cycloalkylidene group include cyclopentylidene, cyclohexylidene, cycloheptylidene, and cyclododecylidene. The cycloalkylidene group may have a substituent such as an aromatic hydrocarbon group, an alkyl group, or an alkoxy group, for example, and specifically may be substituted with an alkyl group having 1 to 4 carbon atoms by about 1 to 3. Specific examples thereof include 3-methylcyclohex-1-ylidene and 3,3, 5-trimethylcyclohex-1-ylidene. Furthermore, such a cycloalkylidene group may be condensed with an aromatic hydrocarbon group, for example, within a range not impairing the effect of the present invention. Specific examples thereof include fluoren-9-ylidene and the like.

In the above formulae (1) to (3), when X is a phenylene group, specific examples of the phenylene group include a 1, 4-phenylene group and a 1, 3-phenylene group. The phenylene group may have a substituent such as an aromatic hydrocarbon group, an alkyl group, or an alkoxy group as long as the effect of the present invention is not impaired.

Preferred examples of X in the above formulae (1) to (3) include a single bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, an alkylidene group having 1 to 4 carbon atoms which may have a substituent, and a cycloalkylidene group having 5 to 15 carbon atoms which may have a substituent.

Among them, more preferable examples of X include a single bond, methylene, ethylene, ethylidene, propylidene, isopropylidene, butylidene, phenylmethylene, 1-phenyleth-1-ylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclododecylidene, 4-methylcyclohex-1-ylidene, 3, 5-trimethylcyclohex-1-ylidene, and fluoren-9-ylidene.

The polycarbonate oligomer represented by the formula (1) and/or the formula (2) and/or the formula (3) can be produced by any conventionally known production method. Specific examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, a solid-phase transesterification method of a prepolymer, and the like. Among them, the interfacial polymerization method, the melt transesterification method, and the solid-phase transesterification method of a prepolymer are industrially advantageous. Among these methods, a melt transesterification method using no phosgene or a solid-phase transesterification method of a prepolymer by the melt transesterification method is particularly preferable.

The above production method is carried out using a dihydroxy compound represented by the following formula (4) and a carbonate forming agent.

[ chemical formula 7]

R in (formula (4))₁～R₄And X is as defined in the above formulae (1), (2) and (3). )

< dihydroxy Compound represented by formula (4) >)

Specific examples of the dihydroxy compound represented by formula (4) include dihydroxybiphenyl compounds such as 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxyphenyl) -1-phenylethane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, and 4, 4' -dihydroxybiphenyl, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 1-bis (4-hydroxyphenyl) ethane, 1-bis (4-hydroxyphenyl) methane, or an isomer mixture of 1, 1-bis (hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) cyclododecane, and 1, 1-bis (4-hydroxyphenyl) -3-methylcyclohexane and the like.

In the polymerization reaction, the dihydroxy compound represented by formula (4) may be used alone, or 2 or more kinds thereof may be mixed at an arbitrary ratio. When a dihydroxy compound other than the dihydroxy compound represented by formula (4) is used, the proportion of the starting material for copolymerization of a hydroxy compound other than the dihydroxy compound represented by formula (4) in the total aromatic dihydroxy compound is in the range of 0 to 90 mol%, preferably 0 to 85 mol%, more preferably 0 to 80 mol%.

In the present invention, the weight average molecular weight of the polycarbonate oligomer represented by formula (1) and/or formula (2) and/or formula (3) is in the range of 500 to 10,000, preferably 600 to 9,000, more preferably 800 to 8,500, and still more preferably 1,000 to 8,000.

< about carbonate Forming Agents >

Specific examples of the Carbonate-forming agent to be reacted with the dihydroxy compound represented by formula (4) include diaryl carbonates such as diphenyl Carbonate, ditolyl Carbonate and Bis (m-cresyl) Carbonate, dialkyl carbonates such as dimethyl Carbonate, diethyl Carbonate and dicyclohexyl Carbonate, alkylaryl carbonates such as methylphenyl Carbonate, ethylphenyl Carbonate and cyclohexylphenyl Carbonate, and diene carbonates such as divinyl Carbonate, diisopropenyl Carbonate and diallyl Carbonate, and carbonic acid. Further, a dihalogenated carbonyl compound such as phosgene, triphosgene, or the like can be cited. Among these, diaryl carbonates are preferred, and diphenyl carbonate is particularly preferred.

< about the molten transesterification method >

The melt transesterification method is explained as a method for producing a polycarbonate oligomer represented by formula (1) and/or formula (2) and/or formula (3).

The melt transesterification reaction is carried out by using a dihydroxy compound represented by formula (4) and diphenyl carbonate as a carbonate-forming agent, stirring the mixture while heating the mixture in the presence of a catalyst under an inert gas atmosphere at normal pressure or reduced pressure, and distilling the produced phenol. In general, the polycarbonate oligomer represented by the formula (1) and/or the formula (2) and/or the formula (3) having a desired molecular weight and a desired amount of terminal hydroxyl groups can be obtained by adjusting the mixing ratio of the dihydroxy compound represented by the formula (4) and the carbonate-forming agent or the degree of reduced pressure during the transesterification reaction.

In order to obtain the polycarbonate oligomer represented by the formula (1) and/or the formula (2) and/or the formula (3), the mixing ratio of the dihydroxy compound represented by the formula (4) and the carbonate forming agent is usually 0.2 to 5 mol times, preferably 0.3 to 3.3 mol times, and more preferably 0.4 to 2.5 mol times, relative to 1 mol of the dihydroxy compound represented by the formula (4).

In the melt transesterification reaction, a transesterification catalyst may be used if necessary in order to increase the reaction rate. The transesterification catalyst is not particularly limited, and for example, the following known transesterification catalysts can be used: alkali metal compounds such as inorganic alkali metal compounds including hydroxides, carbonates, and hydrogen carbonate compounds of lithium, sodium, and cesium, and organic alkali metal compounds such as alcoholates and organic carboxylates; alkaline earth metal compounds such as hydroxides of beryllium, magnesium and the like, inorganic alkaline earth metal compounds such as carbonates and the like, alcoholates, organic alkaline earth metal compounds such as organic carboxylates and the like; basic boron compounds such as sodium salts, calcium salts, and magnesium salts of tetramethylboron, tetraethylboron, and butyltriphenylboron; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine, and basic phosphorus compounds such as quaternary phosphonium salts derived from these compounds; basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide; amine compounds such as 4-aminopyridine, 2-dimethylaminoimidazole and aminoquinoline. Among them, alkali metal compounds are preferable, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferable.

The amount of the catalyst to be used is not limited to the range in which the quality of the oligomer to be produced is not deteriorated due to the catalyst residue, and the amount to be added is not limited to any specific one, and may be, for example, generally 0.05 to 100. mu. mol, preferably 0.08 to 50. mu. mol, more preferably 0.1 to 20. mu. mol, and still more preferably 0.1 to 5. mu. mol, based on 1 mol of the dihydroxy compound represented by the formula (B). The catalyst may be added as it is or dissolved in a solvent and then added, and as the solvent, for example, water, phenol, or the like which does not affect the reaction is preferable.

The reaction conditions for the melt transesterification reaction are usually in the range of 120 to 360 ℃, preferably 150 to 280 ℃, and more preferably 180 to 260 ℃. If the reaction temperature is too low, the transesterification reaction does not proceed, and if the reaction temperature is high, side reactions such as decomposition reaction proceed, which is not preferable. The reaction is preferably carried out under reduced pressure. The reaction pressure is preferably a pressure at which the carbonate forming agent as a raw material is not distilled out of the system and a by-product such as phenol can be distilled out at the reaction temperature. Under such reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

< ingredient (B) >, relating to the present invention

The component (B) contained in the epoxy resin composition of the present invention is a polyepoxy compound having 2 or more epoxy groups in 1 molecule. It is called a so-called prepolymer (intermediate product) and has a low molecular weight while having 2 or more epoxy groups in 1 molecule. Then, the epoxy resin composition of the present invention can be cured (polymerized) as described later to obtain an epoxy resin cured product as a cured product.

The component (B) contained in the epoxy resin composition of the present invention is preferably a polyepoxy compound having a chemical structure represented by the following formula (5).

[ chemical formula 8]

(Y in the formula (5) independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms or a phenylene group, and m is 0 or an integer of 1 to 10.)

Preferred examples of Y in the above formula (5) include an alkylidene group having 1 to 5 carbon atoms and an alkylene group having 1 to 5 carbon atoms, and specific examples thereof include methylene, ethylidene, isopropylidene, propan-1-ylidene, butan-2-ylidene, butan-1-ylidene, 3-methylbutan-2-ylidene, and 2-methylpentan-4-ylidene.

Examples of the polyepoxide represented by the above formula (5) include compounds obtained by reacting a polyhydric compound corresponding to the chemical structure of the polyepoxide with epihalohydrin such as epichlorohydrin. Specific examples of the polyhydric compound as a raw material of the polyepoxide represented by the above formula (5) include 2, 2-bis (4-hydroxyphenyl) propane (bisphenol a), 2-bis (4-hydroxyphenyl) ethane (bisphenol E), 2-bis (4-hydroxyphenyl) methane (bisphenol F), and 4, 4' -dihydroxybiphenyl.

Specific examples of the polyhydric hydroxyl compound as a raw material of the polyepoxy compound other than the polyepoxy compound represented by formula (5) include phenol novolac resins, cresol novolac resins, biphenol novolac resins, and the like.

Specific examples of the polyepoxide compound as the component (B) in the present invention include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, xylene novolac type epoxy resins, triglycidyl isocyanurate, alicyclic epoxy resins, dicyclopentadiene novolac type epoxy resins, and biphenyl novolac type epoxy resins, and in addition, known epoxy resins such as the epoxy resins represented by the following formulae described in JP-A-01-98613 and the like can be cited. In the following formulae, a is an integer of 1 or more and b is a positive number of 1 or less.

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

These epoxy resins may be used in a mixture of 1 or 2 or more.

The method for obtaining the polyepoxide compound as the component (B) of the present invention is not particularly limited, but the following methods are known, for example: 1) an epoxidation reaction of a polyol by dissolving a polyol as a raw material in epihalopropane (Epihalohydrin), reacting the resulting solution using a quaternary ammonium salt such as tetramethylammonium chloride or trimethylbenzylammonium chloride as a catalyst, and then adding a basic compound such as an alkali metal hydroxide as it is and/or as an aqueous solution to the reaction mixture to further react the reaction mixture, or 2) dissolving a raw polyol in epihalopropane such as epichlorohydrin, adding a polar solvent such as methanol or ethanol to the reaction mixture, adding a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to the reaction mixture to react the reaction mixture, or reacting the solid while adding the solid, or 3) continuously distilling water and epihalopropane from the reaction system under reduced pressure or normal pressure while adding an alkali metal hydroxide to the reaction mixture using an aqueous solution of an alkali metal hydroxide, a method of separating the reaction mixture, removing water, and continuously returning epihalohydrin to the reaction system, 4) a method of reacting a raw material polyol with a vinyl halide compound such as allyl chloride or allyl bromide in a solvent in the presence of a base, and then, after the reaction is completed, directly reacting an oxidizing agent capable of oxidizing a carbon-carbon double bond to an epoxy group such as m-chloroperoxybenzoic acid, or for example, a method of mixing a reaction solution with water, taking out a reaction product, then reacting the reaction product with the oxidizing agent, and thereafter, for example, decomposing the remaining oxidizing agent as necessary, and then, concentrating the resultant to obtain a diepoxy compound. In order to obtain the polyepoxy compound having 2 or more epoxy groups in the molecule of 1 in the present invention, the above-mentioned method may be used, and other methods than the above-mentioned may also be used.

In the production of the polyepoxide compound of the present invention, a small amount of oligomer such as dimer, trimer or tetramer is by-produced simultaneously with the progress of the epoxidation reaction, and the polyepoxide compound used in the present invention may contain a small amount of oligomer. The polyepoxide compound used in the present invention may contain, in a small amount, at the time of epoxidation reaction: and compounds having a terminal group having a hydrolyzable chlorine in a state where an epoxy group is not formed.

< optional component >

The epoxy resin composition of the present invention may contain any component in addition to the above-mentioned components (a) and (B) within a range not significantly impairing the effects of the present invention. Examples of the optional components include a curing accelerator, a coupling agent, a flame retardant, an inorganic filler, a resin, a catalyst, a leveling agent, an antifoaming agent, an ion scavenger, a stress relaxation agent, a dye, and a colorant. These optional components may be contained in 1 kind alone, or may be contained in 2 or more kinds in an arbitrary ratio and combination.

As the curing accelerator, any one may be used as long as the effect of the present invention is not significantly impaired, and examples thereof include imidazoles such as tertiary amine compounds, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole, organic sulfonium compounds (sulfine), phosphorus compounds, tetraphenylborate salts and derivatives thereof.

Any coupling agent may be used as long as the effect of the present invention is not significantly impaired, and examples thereof include epoxysilane, aminosilane, ureidosilane, vinylsilane, alkylsilane, organotitanate, and aluminum alkylate.

As the flame retardant, any substance can be used as long as the effect of the present invention is not significantly impaired, and examples thereof include red phosphorus, phosphoric acid esters, melamine derivatives, compounds having a triazine ring, cyanuric acid derivatives, nitrogen-containing compounds of isocyanuric acid derivatives, phosphorus-containing nitrogen compounds such as cyclophosphazene, metal compounds such as zinc oxide, iron oxide, molybdenum oxide, and ferrocene, antimony oxides such as antimony trioxide, antimony tetraoxide, and antimony pentaoxide, and brominated epoxy resins.

As the inorganic filler, any of various materials can be used as long as the effect of the present invention is not significantly impaired, and examples thereof include powders of fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, aluminum nitride, boron nitride, beryllium oxide, forsterite, talc, spinel, mullite, titanium dioxide, and the like, beads formed by spheroidizing these, glass fibers, and the like. By containing the inorganic filler, the moisture absorption, thermal conductivity and adhesiveness of the epoxy resin cured product obtained using the epoxy resin composition can be improved, and the thermal expansion coefficient can be reduced.

As the inorganic filler, any inorganic filler may be used as long as the effect of the present invention is not significantly impaired, and for example, aluminum hydroxide, magnesium hydroxide, zinc silicate, zinc molybdate, and the like may be contained. By containing these substances, the flame-retardant effect can be improved.

The ion scavenger may be any substance as long as the effect of the present invention is not significantly impaired, and examples thereof include hydrotalcites, hydrated oxides of elements such as magnesium, aluminum, titanium, zirconium, and bismuth, and the like. By containing the ion scavenger, the moisture resistance and high-temperature storage property (heat resistance) of an electronic device using the obtained epoxy resin composition can be improved.

As the stress relaxation agent, any substance may be used as long as the effect of the present invention is not significantly impaired, and examples thereof include silicone rubber powder and the like. Further, as the colorant, any colorant may be used as long as the effect of the present invention is not significantly impaired, and examples thereof include carbon black and the like.

The epoxy resin composition of the present invention contains the polycarbonate oligomer as the component (a) as a curing agent, but may be used in combination with a known epoxy curing agent within a range not impairing the effects of the present invention. Examples of the known epoxy curing agent include phenols such as phenol novolac resin, cresol novolac resin, bisphenol a and bisphenol F, acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and pyromellitic anhydride, and amines such as diaminodiphenylmethane, diaminodiphenylsulfone and dicyandiamide. The polycarbonate oligomer as the component (A) is preferably blended in an amount of 1 wt% or more, more preferably 3 wt% or more, and particularly preferably 5 wt% or more, based on the total amount of all the curing agents used. When the amount of the polycarbonate oligomer as the component (A) is small, the effect of improving the physical properties of the resulting cured product is small, which is not preferable. Therefore, the blending amount of the polycarbonate oligomer as the component (a) in the entire curing agent is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and particularly preferably 95% by weight or more.

< about the mixing ratio of the component (A) and the component (B) >)

The epoxy resin composition of the present invention is cured by the reaction of the hydroxyl group and the carbonate group of the component (a) and the epoxy group of the component (B). The mixing ratio of the component (a) and the component (B) is adjusted so that the ratio of the number of moles of epoxy groups of the component (B) to the total number of moles of hydroxyl groups and carbonate groups of the component (a), i.e., (the number of moles of epoxy groups of the component (B)/(the total number of moles of hydroxyl groups and carbonate groups of the component (a)) is usually 0.5 to 10, preferably 0.9 to 5, more preferably 0.95 to 1.05, and particularly preferably 1, from the viewpoint of chemical equivalents.

< about the mixing of the component (A) and the component (B) >

The epoxy resin composition of the present invention contains optional components as required in addition to the components (a) and (B), and it is necessary to uniformly mix them before curing. When the polycarbonate oligomer as the component (A) of the present invention is a solid, it is particularly necessary to cure the polycarbonate oligomer after it is mixed uniformly. The method and apparatus for mixing these substances are not particularly limited as long as they can uniformly disperse and mix these components without significantly impairing the effects of the present invention. However, it is usually sufficient to weigh a predetermined amount of these components and allow them to exist in the same system, and then disperse and mix them by using, for example, a ball mill, a two-roll mill, a three-roll mill, a vacuum kneader, a tank mill, a compound mixer, or the like.

< method for curing >

As a method for curing the epoxy resin composition of the present invention, a conventionally known method for curing an epoxy resin can be used, and for example, the method can be performed by curing an epoxy resin composition by heating and/or irradiating with light.

The heating temperature and the heating time when the epoxy resin composition is heated are not particularly limited, and are preferably appropriately determined according to the formulation of the epoxy resin composition. When the epoxy resin composition is heated, it is preferable to heat the epoxy resin composition while raising the temperature stepwise. Specifically, the polycarbonate oligomer as the component (A) and the polyepoxide as the component (B) of the present invention are generally uniformly mixed while being heated and melted at 60 to 180 ℃ for 1 to 10 hours (preferably 150 ℃ C., 6 hours), and an arbitrary component such as a curing accelerator is added and mixed to prepare an epoxy resin composition. Then, the obtained epoxy resin composition is subjected to pre-forming curing at 100 to 200 ℃ for 0.1 to 60 minutes (preferably 6MPa, 180 ℃ C., 30 minutes) under pressure, and post-curing is carried out at 70 to 200 ℃ for 0.1 to 10 hours (preferably 180 ℃ C., 4 hours) to further improve the curing performance. When the viscosity of the epoxy resin composition is low, the epoxy resin composition may be polymerized by heating at 50 to 150 ℃ (preferably 150 ℃) before the preform is cured, for the purpose of thickening.

< use of epoxy resin composition >

The epoxy resin composition of the present invention contains a polycarbonate oligomer represented by formula (1) and/or formula (2) and/or formula (3) and having a specific weight average molecular weight, and thus not only heat resistance but also dielectric properties are improved, and industrially advantageous effects are exhibited.

The epoxy resin composition of the present invention is useful as a semiconductor sealing material, an electrical insulating material, a resin for a copper clad laminate, a resist, a sealing resin for an electronic product, a resin for a liquid crystal filter, a coating material, various coating agents, an adhesive, a laminate material, and an FRP.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In addition, the weight average molecular weight (Mw) in the following examples was measured by gel permeation chromatography. The analytical method is as follows.

< analytical method >

1. Gel permeation chromatography assay

The device comprises the following steps: HLC-8320GPC, TOSOH

Flow rate: 0.35ml/min, mobile phase: tetrahydrofuran, injection amount: 10 μ l

Pipe column: TSKgel guard column SuperMP (HZ) -N, TSKgel Super Multipore HZ-Nx 3

A detector: RI (Ri)

The analysis method comprises the following steps: the relative molecular weight is expressed in terms of polystyrene.

Polystyrene sample: TOSOH A-500, A-2500, A-5000, F-1, F-2, F-4

2. Determination of the concentration of terminal hydroxyl groups

Use of¹H-NMR was carried out by using TCE (1,1,1, 2-tetrachloroethane) as an internal standard and bisphenol A and bisphenol C as samples, and preparing a calibration curve of the weight ratio to TCE. The weight of the phenol end was determined from the calibration curve.

The device comprises the following steps: AscendTM 400, manufactured by BRUKER Inc

The measurement conditions were as follows: room temperature, cumulative frequency 120 times

3. Dynamic viscoelasticity measurement

A measuring device: EXSTAR DMS6100(Hitachi High-Tech Science Co., Ltd.)

4. Relative dielectric constant and dielectric loss tangent

A measuring device: PNA-LNetwork Analyzer N5230A (Agilent Technologies, Inc.)

CP431 for cavity resonator 1GHz (manufactured by Kanto electronic application development Co., Ltd.)

Reference example 1 Synthesis of polycarbonate oligomer of > 1, 1-bis (4-hydroxyphenyl) cyclododecane

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

(in the formula, n is each independently an integer of 1 or more.)

A four-necked flask equipped with a thermometer, a stirrer and a cooler was charged with 477g (1.4 mol) of 1, 1-bis (4-hydroxyphenyl) cyclododecane and 203g (1.0 mol) of diphenyl carbonate, and after nitrogen substitution in the reaction vessel, 0.1g of a 0.1% cesium carbonate aqueous solution was added thereto at 90 ℃. After the temperature was raised to 200 ℃ and then reduced in pressure, the reaction was carried out while distilling off the formed phenol to obtain 470g of a polycarbonate oligomer of 1, 1-bis (4-hydroxyphenyl) cyclododecane represented by at least 1 or more of the above chemical structural formulae, wherein the reaction was carried out at 13.3kPa for 4 hours, at 1.3kPa for 1 hour, at 230 ℃ and at 0.3kPa for 1 hour, and at 240 ℃ and at 0.3kPa for 2 hours. The weight average molecular weight of the resulting polycarbonate oligomer was 2423 (gel permeation chromatography), and the terminal hydroxyl group concentration was 1.62 mmol/g.

Example 1 epoxy resin composition Using polycarbonate oligomer of "reference example 1

100g of bisphenol A epoxy resin (manufactured by Mitsubishi chemical corporation) having an epoxy equivalent of 184 to 194 and 149g of the polycarbonate oligomer obtained in reference example 1 were weighed and mixed by heating at about 150 ℃ for about 6 hours using a planetary mixer. After cooling to room temperature, 50g of the mixture were separated off and charged to a two-roll mill at 110 ℃. To this was added 0.4g of triphenylphosphine, and kneading was carried out for 3 minutes. The mixture was charged into a male mold of 100mm × 100mm, and pressed by a compression molding machine under conditions of 180 ℃ × 30 minutes × 6 MPa. The formed sheet was post-cured in a hot air circulation oven at 180 ℃ for 4 hours. The cured plate thus obtained was subjected to cutting, and physical properties were measured.

The result of dynamic viscoelasticity measurement of the cured plate based on Japanese Industrial Standard JISK7171 showed that the glass transition temperature (Tg) was 175 ℃. Further, the relative dielectric constant and the dielectric loss tangent were measured by using ASTM D250 as a reference, and the relative dielectric constant was 2.68 and the dielectric loss tangent was 0.0132.

< reference example 2 > Synthesis of polycarbonate oligomer of bisphenol A

A four-necked flask equipped with a thermometer, a stirrer and a cooler was charged with 425.4g (1.9 mol) of 2, 2-bis (4-hydroxyphenyl) propane and 280g (1.3 mol) of diphenyl carbonate, and after nitrogen substitution in the reaction vessel, 0.57g of a 0.2% cesium carbonate aqueous solution was added thereto at 90 ℃. After the temperature was raised to 210 ℃, the reduced pressure was adjusted to 0.6kPa, and the reaction was carried out for 8 hours while distilling off the produced phenol to obtain 510g of the objective polycarbonate oligomer. The weight-average molecular weight of the resulting polycarbonate oligomer was 2210 (gel permeation chromatography), and the terminal hydroxyl group concentration was 1.30 mmol/g.

< comparative example 1 > epoxy resin composition Using polycarbonate oligomer of "reference example 2

100g of bisphenol A epoxy resin (manufactured by Mitsubishi chemical corporation) having an epoxy equivalent of 184 to 194 and 114g of the polycarbonate oligomer obtained in reference example 2 were weighed and mixed by heating at about 150 ℃ for about 6 hours using a planetary mixer. After cooling to room temperature, 50g of the mixture were separated off and charged to a two-roll mill at 110 ℃. To this was added 0.4g of triphenylphosphine, and kneading was carried out for 3 minutes. The mixture was placed in a hot air circulation oven at 130 ℃ and held for 25 minutes to tackify it. The mixture was charged into a male mold of 100mm × 100mm, and pressed by a compression molding machine under conditions of 180 ℃ × 30 minutes × 6 MPa. The formed sheet was post-cured in a hot air circulation oven at 180 ℃ for 4 hours. The cured plate thus obtained was subjected to cutting, and physical properties were measured.

The result of dynamic viscoelasticity measurement of the cured plate based on Japanese Industrial Standard JISK7171 showed that the glass transition temperature (Tg) was 122 ℃. Further, the relative dielectric constant and the dielectric loss tangent were measured by using ASTM D250 as a reference, and the relative dielectric constant was 2.82 and the dielectric loss tangent was 0.0150.

The results of example 1 and comparative example 1 confirmed that the epoxy resin composition of the present invention produced a cured product having a significantly higher glass transition temperature than the conventionally known epoxy resin compositions, and excellent not only heat resistance but also dielectric properties.