WO2016208667A1 - Epoxy resin composition and cured product thereof - Google Patents

Abstract

Provided is an epoxy resin composition that has well-balanced copper foil adhesiveness, mechanical strength, heat resistance and dielectric characteristics (in particular, relative permittivity and dielectric tangent) and is useful in printed wiring boards for electronic appliances, etc. Also provided is a cured product using the epoxy resin composition. The epoxy resin composition comprises a maleimide resin represented by formula (1) and an epoxy resin, wherein the content of the polymaleimide resin is 5-50 wt% relative to the total resin amount in the composition. In formula (1): Rs exist independently and represent a hydrogen atom or an alkyl or aromatic group having 1-5 carbon atoms; a is 1-4; b is 1-3; and n is an integer that satisfies the requirement 1 < the average value of n ≤ 5.

Description

Epoxy resin composition and cured product thereof

The present invention relates to an epoxy resin composition and a cured product thereof. Specifically, for high-reliability semiconductor encapsulant use, electrical / electronic component insulation material use, and various composite materials use such as laminate (printed wiring glass fiber reinforced composite material) and CFRP (carbon fiber reinforced composite material), The present invention relates to an epoxy resin composition useful for various adhesive applications, various coating applications, structural members, and the like, and a cured product thereof.

In general, printed circuit boards for electrical and electronic equipment, especially as a substrate for laminating copper foil, has been conventionally thermosetting, mainly paper-based paper-phenolic resin, glass cloth-based glass cloth-epoxy resin, etc. Resin is used. These thermosetting resins exhibit high heat resistance and dimensional stability due to their unique cross-linking structure, so they are widely used in fields that require high reliability such as electronic parts, especially copper-clad laminates. In the board and interlayer insulation materials, due to the recent demand for higher density, high copper foil adhesion for forming fine wiring and mechanical strength and toughness when drilling or punching is required. It is said that. Although epoxy resin has relatively good mechanical strength and heat resistance, it is required to improve the heat resistance due to the recent high-density mounting of printed wiring boards and high-layer structures, and to improve the mechanical strength of the resin by making the board thinner. It is like that. In addition, a semiconductor chip having a high processing capability such as a CPU is mounted on a laminated plate made of a polymer material. However, as the speed of an element such as a CPU increases and the clock frequency increases, signal propagation delay and transmission are increased. Loss is a problem. Therefore, a low dielectric constant and a low dielectric loss tangent are required for the wiring board.

Conventionally, a bismaleimide resin has been studied as an impregnation resin instead of an epoxy resin for the purpose of improving the dielectric constant of the resin. For example, in Patent Document 1, a wiring board using BT resin, which is a resin in which a bisphenol A-type cyanate ester compound and a bismaleimide compound are used together, is excellent in heat resistance, chemical resistance, electrical characteristics, etc., and is widely used as a high-performance wiring board. in use.

Japanese Patent Publication No.54-30440 Japanese Unexamined Patent Publication No. 2009-001783 Japanese Unexamined Patent Publication No. 2008-208201

A bismaleimide resin, which is a thermosetting resin, is a resin that has excellent low dielectric properties, flame retardancy, and heat resistance, but generally has a problem of lower interlayer adhesion and mechanical strength than epoxy resins.
The present inventors further improved the maleimide resin (Patent Documents 2 and 3) that have been developed so far, and an epoxy resin balanced in copper foil adhesion, heat resistance, and dielectric properties (relative dielectric constant, dielectric loss tangent). The compounding quantity of the maleimide resin in the composition was found.
An object of the present invention is to provide a maleimide resin-containing epoxy resin composition and a cured product thereof balanced in copper foil adhesion, heat resistance, and dielectric properties (relative dielectric constant, dielectric loss tangent). .

As a result of intensive studies to solve the above problems, the present inventors have come to solve the present invention. That is, the present invention

(1) An epoxy resin composition containing a maleimide resin and an epoxy resin represented by the following formula (1), wherein the maleimide resin is contained in an amount of 5 to 50% by weight based on the total amount of the resin in the composition. Epoxy resin composition,

(In the formula (1), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aromatic group. A represents 1 to 4; b represents 1 to 3; N represents an integer, and 1 <n represents an average value ≦ 5.)
(2) The epoxy resin composition according to item (1), which contains a curing accelerator,
(3) The epoxy resin composition according to (1) or (2) above, which contains an epoxy resin curing agent having a phenol group, amino group, acid anhydride or cyanate group in the molecule;
(4) The epoxy resin composition according to any one of (1) to (3) above, which contains a compound having an allyl group or a methallyl group,
(5) A cured product obtained by curing the epoxy resin composition according to the above (1) to (4),
About.

エ ポ キ シ The epoxy resin composition of the present invention has excellent properties in terms of adhesion to metal foil, heat resistance, low dielectric properties, and low dielectric loss tangent properties while containing a maleimide resin. Further, the cured product can provide a prepreg or a laminate having excellent performance.

It is a graph which shows the relationship between content (addition) of maleimide resin in an epoxy resin composition, and bending strength in an Example. It is a graph which shows the relationship between the content (addition) of maleimide resin in an epoxy resin composition in an Example, and peel strength.

The epoxy resin composition of the present invention will be described below.
The epoxy resin composition of the present invention contains a maleimide resin represented by the following formula (1) and an epoxy resin as at least essential components, and the maleimide resin is added in an amount of 5 to 50% by weight based on the total amount of the resin in the composition. %contains.

(In the formula (1), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aromatic group. A represents 1 to 4; b represents 1 to 3; N represents an integer, and 1 <n represents an average value ≦ 5.)

In the epoxy resin composition of the present invention, the method for producing the maleimide resin represented by the formula (1) that can be used is not particularly limited, and it may be produced by any known method known as a method for synthesizing a maleimide compound.
When the maleimide resin of the formula (1) is produced, a compound of the following formula (2) is required as a precursor thereof. For example, in Japanese Patent Laid-Open No. 3-100016 and Japanese Patent Publication No. 8-16151 Describes the reaction of anilines with dihalogenomethyl compounds and dialkoxymethyl compounds. The same method is used to react anilines with bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls. This gives the compound of formula (2).

(In Formula (2), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aromatic group. A represents 1 to 4; b represents 1 to 3; N represents an integer, and 1 <n represents an average value ≦ 5.)

Examples of anilines used in the production of the compound of formula (2) include aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2 , 3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-propylaniline, 3-propylaniline 4-propylaniline, 2-isopropylaniline, 3-isopropylaniline, 4-isopropylaniline, 2-ethyl-6-methylaniline, 2-sec-butylaniline, 2-tert-butylaniline, 4-butylaniline, 4 -Sec-butylaniline, 4-tert-butylaniline, 2,6-die Alkyl-substituted anilines having one or more alkyl groups having 1 to 5 carbon atoms such as ruaniline, 2-isopropyl-6-methylaniline, 4-pentylaniline, phenyl having phenyl groups such as 2-aminobiphenyl, 4-aminobiphenyl, etc. Examples include aniline. These may be used alone or in combination of two or more.

Examples of the bishalogenomethyl biphenyls or bisalkoxymethyl biphenyls used include 4,4′-bis (chloromethyl) biphenyl, 4,4′-bis (bromomethyl) biphenyl, and 4,4′-bis (fluoromethyl). Biphenyl, 4,4'-bis (iodomethyl) biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, 4,4'-dipropoxymethylbiphenyl, 4,4'-diisopropoxy Examples include methylbiphenyl, 4,4′-diisobutoxymethylbiphenyl, 4,4′-dibutoxymethylbiphenyl, 4,4′-di-tert-butoxymethylbiphenyl, and the like. These may be used alone or in combination of two or more. The amount of bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls used is preferably 0.05 to 0.8 mol, more preferably 0.1 to 0.6 mol, relative to 1 mol of the aniline used. .

In the reaction, if necessary, an acidic catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid and the like may be used. These may be used alone or in combination of two or more. The amount of the catalyst used is preferably 0.1 to 0.8 mol, more preferably 0.5 to 0.7 mol with respect to 1 mol of the aniline used. If the amount is too large, the viscosity of the reaction solution is high. If the amount is too small, the reaction proceeds slowly.
The reaction may be carried out using an organic solvent such as toluene or xylene, if necessary, or without solvent. For example, after adding an acidic catalyst to a mixed solution of anilines and a solvent, when the catalyst contains water, the water is removed from the system by azeotropic distillation. Thereafter, bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls are preferably added at 40 to 100 ° C., more preferably 50 to 80 ° C., preferably over 1 to 5 hours, more preferably 2 to 4 hours, and then the solvent is added. The temperature is raised while removing from the system, and the reaction is preferably carried out at 180 to 240 ° C., more preferably 190 to 220 ° C., preferably 5 to 30 hours, more preferably 10 to 20 hours. After completion of the reaction, neutralize the acidic catalyst with an aqueous alkaline solution, add a water-insoluble organic solvent to the oil layer and repeat washing until the wastewater becomes neutral, and distill off excess anilines and organic solvent under heating and reduced pressure. This gives the compound of formula (2). Although not mentioned in Japanese Patent Publication No. 8-16151 and Japanese Patent No. 5030297, diphenylamine, which is a by-product at this stage, varies depending on the amount of catalyst, the ratio of raw materials used, temperature, time, etc. Usually 2 to 10% by weight is contained in the resin. Diphenylamine cannot be removed under conditions where aniline is distilled off. Diphenylamine can be removed by blowing steam or an inert gas such as a large amount of nitrogen gas under reduced pressure by heating at a temperature equal to or higher than the boiling point of aniline.

When diphenylamine is contained in the epoxy resin composition of the present invention, for example, when used for a curing reaction with an epoxy resin, it becomes a terminal end of a molecular chain, and if the content is large, a curing network is not sufficiently formed. There is a possibility that the mechanical strength will be significantly reduced. In addition, when diphenylamine is contained in the aromatic amine resin represented by the formula (2), diphenylamine remains as it is after maleimidation and remains in the cured product as it is without contributing to the reaction. Bleed out and thermal decomposition resistance may decrease. Accordingly, the diphenylamine content is preferably 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.2% by weight or less.

The softening point of the aromatic amine resin represented by the formula (2) is preferably 65 ° C. or less, and more preferably 60 ° C. or less. When the softening point is higher than 65 ° C., the viscosity of the maleimidized resin becomes high, and it becomes difficult to impregnate carbon fibers or glass fibers. If the dilution solvent is increased to lower the viscosity, the resin may not adhere sufficiently.

The maleimide resin of the formula (1) used in the epoxy resin composition of the present invention can be obtained by reacting the compound of the formula (2) with maleic anhydride in the presence of a solvent and a catalyst. A method described in Japanese Patent Application Laid-Open No. 100016 or Japanese Patent Application Laid-Open No. 61-229863 may be employed. As the solvent used in the reaction, it is necessary to remove water generated during the reaction from the system, and therefore a water-insoluble solvent is used. For example, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, methyl isobutyl ketone and cyclopentanone However, it is not limited to these, and two or more kinds may be used in combination. In addition to the water-insoluble solvent, an aprotic polar solvent may be used in combination. Examples thereof include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc., and two or more kinds may be used in combination. When using an aprotic polar solvent, it is preferable to use a solvent having a higher boiling point than the water-insoluble solvent used in combination. The catalyst is an acidic catalyst and is not particularly limited, and examples thereof include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid.
For example, maleic acid is dissolved in toluene, an N-methylpyrrolidone solution of the compound of formula (2) is added with stirring, and then p-toluenesulfonic acid is added to remove water generated under reflux conditions from the system. While doing the reaction.

Examples of the alkyl group having 1 to 5 carbon atoms in the formula (1) include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, sec- Examples thereof include a butyl group and an n-pentyl group.
Further, the average value of n in the formula (1) can be calculated from the value of the weight average molecular weight obtained by the measurement of gel permeation chromatography (GPC) of the maleimide resin, but is approximately a raw material. It can be considered to be almost equivalent to the average value of n calculated from the GPC measurement result of the amine compound represented by the formula (2).

The epoxy resin composition of the present invention contains a maleimide resin and an epoxy resin represented by the formula (1). The blending amount of the maleimide resin represented by the formula (1) is 5 to 50% by weight with respect to the total amount of the resin in the epoxy resin composition. The amount is preferably 10 to 50% by weight, more preferably 20 to 50% by weight. In the case of the above range, in the physical properties of the cured product, mechanical strength and peel strength are high, dielectric loss tangent is low, and heat resistance tends to be high.

The epoxy resin that can be used in the epoxy resin composition of the present invention includes a monomer containing at least one epoxy group from the viewpoint that the epoxy group has a curing promoting action. Examples of the epoxy resin that can be blended with the maleimide resin represented by the formula (1) include novolak type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin, epoxy Examples include alkoxysilane compounds containing functional groups. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, -(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxymethoxysilane, isobutyltriethoxysilane, isopropyltrimethoxysilane, isopropyltrialkoxysilanes, phenyltrimethoxysilane, phenyltriethoxysilane, 5,6-epoxyhexyltrimethoxy Silane, 9,10-epoxydecyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, etc. Polycondensates and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, glycidyl etherified products derived from alcohols, alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, etc. Examples include, but are not limited to, solid or liquid epoxy resins. These may be used alone or in combination of two or more.

Further, a phenol aralkyl resin obtained by a condensation reaction of phenol and the above bishalogenomethylbiphenyls or bisalkoxymethylbiphenyls is used as a raw material, and is represented by the following formula (3) obtained by a dehydrochlorination reaction with epichlorohydrin. The epoxy resin used is particularly preferable as an epoxy resin that can be blended because it is excellent in low moisture absorption, flame retardancy, and dielectric properties.

(Wherein a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aromatic group. A represents 1 to 4; b represents 1 to 3). n is an integer and represents the average value of 1 <n ≦ 5.

Examples of the alkyl group having 1 to 5 carbon atoms in the formula (3) include the same as those described in the description of the alkyl group having 1 to 5 carbon atoms in the formula (1), and the formula (3) The value of n in it can be calculated from the value of the weight average molecular weight determined by the measurement of gel permeation chromatography (GPC) of the epoxy resin.

The blending amount of the epoxy resin is not particularly limited, but is preferably in the range of 0.1 to 10 times, more preferably 0.3 to 2 times that of the maleimide resin by weight ratio. When the compounding amount of the epoxy resin is 0.1 times or more of the maleimide resin, the cured product is difficult to become brittle, and when it is 10 times or less, the heat resistance and dielectric properties tend to be further improved.

The epoxy resin composition of the present invention can be used in combination with a conventionally known epoxy resin curing agent. Examples of the epoxy resin curing agent that can be used in combination include compounds having a phenol group, benzoxazine, amino group, thiol group, acid anhydride, or cyanate group in the molecule. Specific examples include amine compounds represented by the above formula (2), phenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenylsulfone, diaminodiphenyl sulfide, bis (4-amino-3,5-dimethyl-phenyl). 1,4-diisopropylbenzene, bis (4-aminophenyl) -1,4-diisopropylbenzene, aromatic diamines such as xylenediamine, aliphatic amines such as methylenedianiline, halogenated derivatives thereof, aliphatic Thiols such as methanedithiol, propanedithiol, cyclohexanedithiol, 2-mercaptoethyl-2,3-dimercapto-succinate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), diethyleneglycol Bis (2-mercaptoacetate), 1,2-dimercaptopropyl methyl ether, bis (2-mercaptoethyl) ether, trimethylolpropane tris (thioglycolate), pentaerythritol tetra (mercaptopropionate), pentaerythritol tetra (Thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate), tris-mercaptan derivative of tri-glycidyl ether of propoxylated alkane, and dipentaerythritol poly (β-thiopropioate) A halogen-substituted derivative of an aliphatic thiol; an aromatic thiol such as di-, tris- or tetra-mercaptobenzene, bis-, tris- or tetra- (mercaptoalkyl) ) Benzene, dimercaptobiphenyl, toluene dithiol and naphthalene dithiol; halogen-substituted derivatives of aromatic thiols; heterocycle-containing thiols such as amino-4,6-dithiol-sym-triazine, alkoxy-4,6-dithiol -Sym-triazine, aryloxy-4,6-dithiol-sym-triazine, and 1,3,5-tris (3-mercaptopropyl) isocyanurate; halogen-substituted derivatives of heterocyclic-containing thiols; at least two mercapto A thiol compound having a group and containing a sulfur atom in addition to the mercapto group, for example, bis-, tris- or tetra (mercaptoalkylthio) benzene, bis-, tris- or tetra (mercaptoalkylthio) alkane, bis ( Lucaptoalkyl) disulfide, hydroxyalkylsulfide bis (mercaptopropionate), hydroxyalkylsulfide bis (mercaptoacetate), mercaptoethyl ether bis (mercaptopropionate), 1,4-dithian-2,5-diol bis (mercapto) Acetate), bis (mercaptoalkyl ester) thiodiglycolate, bis (2-mercaptoalkyl ester) thiodipropionate, bis (2-mercaptoalkyl ester) 4,4-thiobutyrate, 3,4-thiophenedithiol, bismuth Thiol and polythiol or polymercaptan curing agent such as 2,5-dimercapto-1,3,4-thiadiazole, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydro Phthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, acid anhydride compounds such as methylhexahydrophthalic anhydride, bisphenols, phenols (phenol, alkyl substituted phenol, aromatic substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde , Cinnamaldehyde, etc.), phenols benzoxazines and various diene compounds Polymers with dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl) Examples thereof include, but are not limited to, polycondensates with isobutyl ketone, acetophenone, benzophenone, etc., and benzoxazine pairs of the polycondensates. Moreover, the compound which has the phenol group mentioned above, a benzoxazine, an amino group, a thiol group, or a cyanate group can be used also as a hardening | curing agent of a maleimide resin. These may be used alone or in combination of two or more.
Moreover, the compound represented by the following formula (4), which is a raw material for the epoxy resin of the formula (3), is particularly preferable as an epoxy resin curing agent because of its excellent low moisture absorption, flame retardancy, and dielectric properties.

(Wherein a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aromatic group. A represents 1 to 4; b represents 1 to 3). n is an integer and represents an average value of 1 <n ≦ 20.

Examples of the alkyl group having 1 to 5 carbon atoms in the formula (4) include the same as those described in the description of the alkyl group having 1 to 5 carbon atoms in the formula (1), and the formula (4) The average value of n can be calculated from the value of the weight average molecular weight determined by the measurement of gel permeation chromatography (GPC) of the epoxy resin.

The compounding amount of the epoxy resin curing agent is preferably not more than twice that of the epoxy resin by weight, and more preferably not more than 1 time.
The epoxy resin composition of the present invention containing an epoxy resin curing agent is adjusted so that the maleimide resin represented by the formula (1) is contained in an amount of 5 to 50% by weight based on the total amount of the resin in the composition. To do. More preferably, it is 10 to 50% by weight, and particularly preferably 20 to 50% by weight. It is. In the case of the above range, in the physical properties of the cured product, mechanical strength is high, peel strength is high, and heat resistance tends to be high.

In the epoxy resin composition of the present invention, a known maleimide compound other than the maleimide resin of the formula (1) can be used in combination as necessary. Specific examples of maleimide compounds that can be used include 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3 , 3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone Examples thereof include, but are not limited to, bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, and 1,3-bis (4-maleimidophenoxy) benzene. These may be used alone or in combination of two or more. The blending amount of the maleimide compound is preferably 5 times or less, more preferably 2 times or less of the maleimide resin of the formula (1) by weight ratio.

The epoxy resin composition of the present invention may contain a cyanate ester compound. A conventionally well-known cyanate ester compound can be used as a cyanate ester compound which can be mix | blended with the epoxy resin composition of this invention. Specific examples of cyanate ester compounds include polycondensates of phenols and various aldehydes, polymers of phenols and various diene compounds, polycondensates of phenols and ketones, and polycondensations of bisphenols and various aldehydes. Examples include, but are not limited to, cyanate ester compounds obtained by reacting a product with cyanogen halide. These may be used alone or in combination of two or more.
In addition, cyanate ester compounds described in Japanese Patent Application Laid-Open No. 2005-264154 are particularly preferable as cyanate ester compounds because they are excellent in low moisture absorption, flame retardancy, and dielectric properties.

The epoxy resin composition of this invention can contain a hardening accelerator as needed.
Examples of curing accelerators that can be used include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole. Such as imidazoles, triethylamine, triethylenediamine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,0) undecene-7, tris (dimethylaminomethyl) phenol, benzyldimethylamine, etc. Phosphines such as amines, triphenylphosphine, tributylphosphine, trioctylphosphine and organometallic salts such as tin octylate, zinc octylate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, tin oleate, Zinc, aluminum chloride, include organometallic compounds such as metal chlorides such as tin chloride, benzoyl peroxide, dicumyl peroxide, there is a methyl ethyl ketone peroxide, etc. t- butyl perbenzoate organic peroxide. If the amount of the curing accelerator is too small, it may cause a curing failure, and if it is too large, the cured material properties of the resin composition may be adversely affected. Therefore, it is preferably added in an amount of 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, based on the maleimide resin.

The epoxy resin composition of this invention can contain the compound which has an allyl group or a methallyl group as needed.
Examples of the compound having an allyl group or methallyl group that can be used include 4,4′-bisphenol A diallyl ether, 4,4′-bisphenol F diallyl ether, 4,4′-bisphenol F dimethallyl ether, tri ( (Meth) allyl isocyanurate, 2,2-di (4-acetyloxy-3- (meth) allylphenyl) propane, di (4-acetyloxy-3- (meth) allylphenyl) methane, di (4-acetyloxy) -3- (meth) allylphenyl) sulfone, 2,2-di (4-benzoyloxy-3- (meth) allylphenyl) propane, di (4-benzoyloxy-3- (meth) allylphenyl) methane, di (4-Benzoyloxy-3- (meth) allylphenyl) sulfone, 2,2-di (4-toluoyloxy-3) (Meth) allylphenyl) propane, di (4-toluoyloxy-3- (meth) allylphenyl) methane, di (4-toluoyloxy-3- (meth) allylphenyl) sulfone, 2,2-di ( 4-propionyloxy-3- (meth) allylphenyl) propane, di (4-propionyloxy-3- (meth) allylphenyl) methane, di (4-propionyloxy-3- (meth) allylphenyl) sulfone, 2 , 2-di (4-butyryloxy-3- (meth) allylphenyl) propane, 2,2-di (4-isobutyryloxy-3- (meth) allylphenyl) propane / allyl chloride, allyl alcohol, allyl ethyl Ether, allyl-2-hydroxyethyl ether, allyl glycidyl ether, methallyl glycidyl ether, diallyl Tallates, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, triallyl isocyanurate. Preferred examples include those represented by the following general formula (5).

(In the formula (5), a plurality of R ₁ and R ₂ each independently exist, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aromatic group. A represents 1 to 4, b Represents 1 to 3. n is an integer and represents an average value of 1 <n ≦ 5.

Examples of the alkyl group having 1 to 10 carbon atoms in R ₁ and R ₂ in the formula (5) include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, tert-butyl, sec-butyl, n-pentyl, i-pentyl, amyl, n-hexyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, decyl A methyl group is preferable.
As the aromatic group in R ₁ and R ₂ in the above formula (5), an aromatic hydrocarbon group such as phenyl group, biphenyl group, indenyl group, naphthyl group, anthryl group, fluorenyl group, pyrenyl group, furanyl group, Examples include thienyl group, thienothienyl group, pyrrolyl group, imidazolyl group, pyridyl group, pyrazyl group, pyrimidyl group, quinolyl group, indolyl group, and carbazolyl group.

In addition, the value of n in the formula (5) is an integer, and represents an average value of 1 <n ≦ 5. n is preferably from 1 to 10, more preferably from 2 to 8, and particularly preferably from 2 to 4. The value of n can be calculated from the value of the weight average molecular weight determined by the gel permeation chromatography (GPC) measurement of the allyl ether resin. It can be considered to be almost equivalent to the value of n calculated from

The weight average molecular weight (Mw) of the compound having an allyl group or a methallyl group is preferably 350 to 1200. More preferably, it is 400 to 1000, and particularly preferably 440 to 800. If the molecular weight is 350 or less, it may be difficult to form a cured product due to volatility, and if the molecular weight is 1200 or more, compatibility with a high viscosity or a solvent may be very difficult. Can be difficult.
In addition, the weight average molecular weight of allyl ether resin can be measured by the gel permeation chromatography method (GPC).

The production method of the compound having an allyl group or methallyl group represented by the formula (5) is not particularly limited, and may be produced by any known method known as a synthesis method of an allyl ether compound. For example, Japanese Patent Application Laid-Open No. 2003-104923 discloses an allyl ether obtained by reacting a polyphenol compound with an allyl halide such as allyl chloride, allyl bromide or methylallyl chloride using a base such as an alkali metal hydroxide. Is disclosed.

In the epoxy resin composition of the present invention, the compounding amount of the compound having an allyl group or a methallyl group can be appropriately set according to the type of the compound to be used, and is not particularly limited. From the viewpoint of the fluidity of the epoxy resin composition and the heat resistance of the cured product obtained by curing the epoxy resin composition, the content of the compound having an allyl group or a methallyl group is 5 to 30% by mass with respect to the total amount of the composition. Preferably, it is 7 to 25% by mass. By setting the content ratio of the compound having an allyl group or methallyl group to 5 to 30% by mass with respect to the total amount of the composition, it is possible to obtain an epoxy resin composition having a relatively low temperature moldability and having a viscosity, Moreover, it exists in the tendency for the hardened | cured material which has high heat resistance to be obtained easily.

Furthermore, a known additive can be blended in the epoxy resin composition of the present invention as necessary. Specific examples of additives that can be used include curing agents for epoxy resins, polybutadiene and modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds , Silicone gel, silicone oil, inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, silane cup Coloring agents such as a surface treatment agent for a filler such as a ring agent, a release agent, carbon black, phthalocyanine blue, and phthalocyanine green can be used. The amount of these additives is preferably 1,000 parts by weight or less, more preferably 700 parts by weight or less, based on 100 parts by weight of the total resin of the resin composition.

The method for preparing the epoxy resin composition of the present invention is not particularly limited, but each component may be mixed evenly or prepolymerized. For example, the maleimide resin and epoxy resin used in the present invention are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, a prepolymer is obtained by adding a maleimide resin used in the present invention and an epoxy resin, and if necessary, a curing agent such as an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives. May be used. For mixing or prepolymerization of each component, for example, an extruder, a kneader, or a roll is used in the absence of a solvent, and a reaction kettle with a stirring device is used in the presence of a solvent.

An organic solvent can be added to the epoxy resin composition of the present invention to obtain a varnish-like composition (hereinafter simply referred to as varnish). If necessary, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain an epoxy resin composition varnish, and glass fiber. A prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding to obtain a cured product of the epoxy resin composition of the present invention. can do. In this case, the solvent is used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material containing a carbon fiber can also be obtained as it is, for example with a RTM system.

In addition, the epoxy resin composition of the present invention can be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is formed by applying the epoxy resin composition of the present invention on the release film as the epoxy resin composition varnish, removing the solvent under heating, and then performing B-staging. Obtained as an adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

A prepreg can be obtained by heating and melting the epoxy resin composition of the present invention to lower the viscosity and impregnating the fiber with a reinforcing fiber such as glass fiber, carbon fiber, polyester fiber, polyamide fiber or alumina fiber.
Moreover, a prepreg can also be obtained by impregnating the varnish into a reinforcing fiber and drying by heating.
The above prepreg is cut into the desired shape, laminated with copper foil, etc. if necessary, and the epoxy resin composition for laminates is heat-cured while applying pressure to the laminate by the press molding method, autoclave molding method, sheet winding molding method, etc. By doing so, a laminated board can be obtained.
Furthermore, a circuit can be formed on a laminated board made by superimposing copper foil on the surface, and a multilayer circuit board can be obtained by superimposing a prepreg or copper foil thereon and repeating the above operation.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these Examples. In the text, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. In the examples, the softening point and melt viscosity were measured by the following methods.
・ Softening point: Measured by a method according to JIS K-7234 ・ Melt viscosity: Viscosity at 150 ° C. by cone plate method ・ Diphenylamine content: Measured by gas chromatography

(Synthesis Example 1)
A flask equipped with a thermometer, a condenser, a Dean-Stark azeotropic distillation trap, and a stirrer was charged with 372 parts of aniline and 200 parts of toluene, and 146 parts of 35% hydrochloric acid was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, the mixture was heated to cool and separate azeotropic water and toluene, and then only the organic layer of toluene was returned to the system for dehydration. Subsequently, 125 parts of 4,4′-bis (chloromethyl) biphenyl was added over 1 hour while maintaining the temperature at 60 to 70 ° C., and the reaction was further carried out at the same temperature for 2 hours. After completion of the reaction, toluene was distilled off while raising the temperature to bring the inside of the system to 195 to 200 ° C., and the reaction was carried out at this temperature for 15 hours. Then, with cooling, 330 parts of 30% aqueous sodium hydroxide solution was slowly added dropwise so that the system did not circulate vigorously, and the toluene distilled off at a temperature of 80 ° C. or lower was returned to the system and allowed to stand at 70 ° C. to 80 ° C. I put it. The separated lower aqueous layer was removed, and the reaction solution was washed with water until the washing solution became neutral. Subsequently, 173 parts of aromatic amine resin (a1) was obtained by distilling off excess aniline and toluene from the oil layer with a rotary evaporator under heating and reduced pressure (200 ° C., 0.6 KPa). Diphenylamine in the aromatic amine resin (a1) was 2.0%.
The obtained resin was again dripped little by little on the rotary evaporator under heating and reduced pressure (200 ° C., 4 KPa) instead of steam blowing. As a result, 166 parts of aromatic amine resin (A1) was obtained. The aromatic amine resin (A1) obtained had a softening point of 56 ° C., a melt viscosity of 0.035 Pa · s, and diphenylamine of 0.1% or less. The average value of n in the formula (2) calculated from the measurement result of gel permeation chromatography was 1.6.

(Synthesis Example 2)
After adding 147 parts of maleic anhydride and 300 parts of toluene to a flask equipped with a thermometer, condenser, Dean-Stark azeotropic distillation trap, and stirrer, cooling and separating the water and toluene azeotropically heated. Then, only toluene which is an organic layer was returned to the system for dehydration. Next, a resin solution obtained by dissolving 195 parts of the aromatic amine resin (A1) obtained in Example 1 in 195 parts of N-methyl-2-pyrrolidone was added over 1 hour while maintaining the system at 80 to 85 ° C. It was dripped. After completion of the dropping, the reaction is carried out at the same temperature for 2 hours, 3 parts of p-toluenesulfonic acid is added, condensed water and toluene azeotroped under reflux conditions are cooled and separated, and only toluene which is an organic layer Was returned to the system and reacted for 20 hours while dehydrating. After completion of the reaction, 120 parts of toluene was added, and washing with water was repeated to remove p-toluenesulfonic acid and excess maleic anhydride, followed by heating to remove water from the system by azeotropy. Next, the reaction solution was concentrated to obtain a resin solution containing 70% of maleimide resin (M1).

(Example 1)
30 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 40 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin curing agent 1 (Nippon Kayaku KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point 65 ° C.) 29 parts by weight, 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) 1 part by weight, kneaded with a mixing roll, and tableted Thereafter, a resin molded body was prepared by transfer molding and cured at 200 ° C. for 2 hours to obtain a cured product of the present invention.

(Example 2)
48 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 30 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin curing agent 1 (Nippon Kayaku KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point 65 ° C.) 21 parts by weight, 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) 1 part by weight, kneaded with a mixing roll, and tableted Thereafter, a resin molded body was prepared by transfer molding and cured at 200 ° C. for 2 hours to obtain a cured product of the present invention.

(Reference Example 1)
56 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 25 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin curing agent 1 (Nippon Kayaku KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point 65 ° C.) 18 parts by weight, 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) 1 part by weight, kneaded with a mixing roll, and tableted Thereafter, a resin molded body was prepared by transfer molding and cured at 200 ° C. for 2 hours to obtain a cured product.

(Comparative Example 1)
56 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin hardener 1 (KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point) 65 parts) and 43 parts by weight of 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.), kneaded with a mixing roll, tableted, prepared by resin molding by transfer molding, 2 hours at 200 ° C And cured.

(Comparative Example 2)
70 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 16 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin curing agent 1 (Nippon Kayaku KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point 65 ° C.) 12 parts by weight, 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) 2 parts by weight, kneaded with a mixing roll, and tableted Thereafter, a resin molded body was prepared by transfer molding and cured at 200 ° C. for 2 hours.

The physical properties of the cured products obtained in Examples 1 and 2 and Comparative Examples 1 and 2 and Reference Example 1 were measured for the following items. The results are shown in Table 1, FIG. 1 and FIG.
Glass transition temperature: Temperature measured by a dynamic viscoelasticity tester and tan δ is the maximum value.
Dielectric constant: (Cavity Resonator Agilent Technologies, Inc.) Measured at 1 GHz according to K6991. Bending strength: Measured at 30 ° C. according to JIS-6481 (bending strength).

As apparent from Table 1 and plotted FIG. 1, the epoxy resin composition of the present invention in which the blending amount of the maleimide resin (M1) represented by the formula (1) is blended in the range of 5 to 50% by weight is It can be seen that the material is superior in mechanical strength adhesion and dielectric loss tangent as compared to the case of the blending amount outside the range.

(Example 3)
30 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 40 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin curing agent 1 (Nippon Kayaku KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point 65 ° C.) 29 parts by weight, 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) 1 part by weight, kneaded with a mixing roll, and tableted Thereafter, a resin molded body was prepared on copper foil by transfer molding and cured at 200 ° C. for 2 hours to obtain a cured product of the present invention.

Example 4
48 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 30 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin curing agent 1 (Nippon Kayaku KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point 65 ° C.) 21 parts by weight, 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) 1 part by weight, kneaded with a mixing roll, and tableted Thereafter, a resin molded body was prepared by transfer molding and cured at 200 ° C. for 2 hours to obtain a cured product of the present invention.

(Comparative Example 3)
56 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin hardener 1 (KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point) 65 parts) and 43 parts by weight of 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.), kneaded with a mixing roll, tableted, prepared by resin molding by transfer molding, 2 hours at 200 ° C And cured.

(Reference Example 2)
56 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2, 25 parts of epoxy resin 1 (Nippon Kayaku NC-3000-L epoxy equivalent 269 g / eq. Softening point 52 ° C.), epoxy resin curing agent 1 (Nippon Kayaku KAYAHARD GPH-65 hydroxyl group equivalent 199 g / eq. Softening point 65 ° C.) 18 parts by weight, 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) 1 part by weight, kneaded with a mixing roll, and tableted Thereafter, a resin molded body was prepared on copper foil by transfer molding and cured at 200 ° C. for 2 hours to obtain a cured product.

The physical properties of the cured products obtained in Examples 3 and 4 and Reference Example 2 and Comparative Example 3 were measured for the following items. The results are shown in Table 2 and FIG.
・ Peel strength: Conforms to JISK-6911

As apparent from Table 2 and plotted FIG. 2, the epoxy resin composition of the present invention in which the blending amount of the maleimide resin (M1) represented by the formula (1) is blended in the range of 5 to 50% by weight is as follows. It can be seen that the material is superior in mechanical strength adhesion as compared with the case of the amount out of the range.

(Synthesis Example 3)
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 40 parts of water, 400 parts of dimethyl sulfoxide, and 210 parts of phenol biphenylene resin (hydroxyl equivalent 210 g / eq. Softening point 74 ° C.) were added while purging with nitrogen. After heating to ℃ and dissolving, cooled to 38-40 ℃, as it is, 44.4 parts of flaky sodium hydroxide (purity 99%, manufactured by Tosoh) (1.1 molar equivalent to 1 molar equivalent of hydroxyl group of phenol biphenylene resin) ) Was added over 60 minutes, and then allyl chloride (purity 98.7 area% commercially available allyl chloride was separated by distillation. Allyl chloride polymer amount <0.2 area% confirmed by gas chromatography (GC)) 101.5 parts (1.3 molar equivalents relative to 1 molar equivalent of hydroxyl group of phenol biphenylene resin, Potassium 1 mole dropwise 1.18 moles) over a period of 60 minutes for, as 5 hours at 38-40 ° C., was subjected to 1 hour at 60 ~ 65 ° C.. After completion of the reaction, after distilling off water, dimethyl sulfoxide, etc. under reduced pressure by heating at 135 ° C. or less with a rotary evaporator, 740 parts of methyl isobutyl ketone was added, and washing with water was repeated to confirm that the aqueous layer became neutral. Then, 240 parts of allyl-modified biphenylaralkyl novolak resin (AEP1) was obtained by distilling off the solvents from the oil layer using a rotary evaporator under nitrogen bubbling under reduced pressure. The total chlorine of the obtained resin was 15 ppm. The obtained resin was semi-solid. The number average molecular weight (Mn) obtained by GPC measurement was 579, and the weight average molecular weight (Mw) was 805. The average value of n in the formula (5) calculated from the measurement result of gel permeation chromatography was 2.0.

(Synthesis Example 4)
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, 25 parts by mass of water, 500 parts by mass of dimethyl sulfoxide, and phenol resin (phenol-biphenylene type hydroxyl group equivalent 200 g / eq. Softening point 65 ° C.) 500 Mass parts were added, and the mixture was heated to 45 ° C. and dissolved. Next, the mixture was cooled to 38 to 40 ° C., and 130.0 parts by mass of flaky caustic soda (purity: 99%, manufactured by Tosoh Corp.) (1.3 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added over 60 minutes. Thereafter, 294.3 parts by mass of methallyl chloride (purity 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) (1.3 molar equivalents relative to 1 molar equivalent of the hydroxyl group of the phenol resin) was added dropwise over 60 minutes, and the temperature was 38 to 40 ° C. For 5 hours and at 60 to 65 ° C. for 1 hour.
After completion of the reaction, water, dimethyl sulfoxide, and the like were distilled off under reduced pressure by heating at 125 ° C. or lower using a rotary evaporator. And 740 mass parts of methyl isobutyl ketone was added, and water washing was repeated, and it confirmed that the water layer became neutral. Then, 600 parts by mass of methallyl-modified biphenylaralkyl novolac resin (MEP1) was obtained by distilling off the solvents from the oil layer using a rotary evaporator while bubbling nitrogen under reduced pressure. The number average molecular weight (Mn) obtained by GPC measurement was 591 and the weight average molecular weight (Mw) was 826. The average value of n in the formula (5) calculated from the measurement result of gel permeation chromatography was 2.0.

(Example 5)
48 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2 and 6 parts of epoxy resin (KBM-403 epoxy equivalent 280 g / eq. Softening point 52 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.), obtained in Synthesis Example 3 44 parts by weight of allyl-modified biphenyl aralkyl novolak resin (AEP1) and 2 parts by weight of 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) were kneaded with a mixing roll, and the gel time at 175 ° C. was measured and cured. Was 64 seconds.

(Example 6)
48 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2 and 6 parts of epoxy resin (KBM-303 epoxy equivalent 280 g / eq. Softening point 52 ° C. manufactured by Shin-Etsu Chemical Co., Ltd.), obtained in Synthesis Example 3 44 parts by weight of allyl-modified biphenylaralkyl novolak resin and 2 parts by weight of 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) were mixed, kneaded with a mixing roll, and measured for gel time at 175 ° C. to evaluate curability. However, it was 59 seconds.

(Example 7)
48 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2 and 6 parts of epoxy resin (KBM-403 epoxy equivalent 280 g / eq. Softening point 52 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.), obtained in Synthesis Example 4 44 parts by weight of the methallyl-modified biphenylaralkyl novolak resin and 2 parts by weight of 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) were mixed, kneaded with a mixing roll, and measured for gel time at 175 ° C. to evaluate curability. However, it was 68 seconds.

(Example 8)
48 parts by weight of maleimide resin (M1) obtained in Synthesis Example 2 and 6 parts of epoxy resin (KBM-303, epoxy equivalent 280 g / eq. Softening point 52 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.), obtained in Synthesis Example 4 44 parts by weight of the methallyl-modified biphenylaralkyl novolak resin and 2 parts by weight of 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) were mixed, kneaded with a mixing roll, and measured for gel time at 175 ° C. to evaluate curability. However, it was 57 seconds.

(Comparative Example 4)
98 parts by weight of the maleimide resin (M1) obtained in Synthesis Example 2 and 2 parts by weight of 2-ethyl 4-methylimidazole (Shikoku Kasei Co., Ltd.) were mixed and kneaded with a mixing roll, and the gel time at 175 ° C. was measured. When the curability was evaluated, it was 900 seconds or longer.

From the above Examples 5 to 8 and Comparative Example 4, it can be confirmed that the epoxy resin composition of the present invention can be cured at a relatively low temperature of 200 ° C. or less and in a short time.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on June 25, 2015 (Japanese Patent Application No. 2015-127282), which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

The epoxy resin composition and the cured product thereof according to the present invention are used for a highly reliable semiconductor encapsulant, an electrical / electronic component insulating material, and a laminate (printed wiring glass fiber reinforced composite material) or CFRP (carbon fiber reinforced composite material). ) And other various composite materials, various adhesives, various paints, structural members, and the like.

Claims (5)

An epoxy resin composition containing a maleimide resin represented by the following formula (1) and an epoxy resin, the epoxy resin composition containing 5 to 50% by weight of the maleimide resin with respect to the total amount of the resin in the composition object.

(In the formula (1), a plurality of R's are present independently and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aromatic group. A represents 1 to 4; b represents 1 to 3; N represents an integer, and 1 <n represents an average value ≦ 5.) The epoxy resin composition according to claim 1 containing a curing accelerator. The epoxy resin composition according to claim 1 or 2, which contains an epoxy resin curing agent having a phenol group, an amino group, an acid anhydride or a cyanate group in the molecule. The epoxy resin composition according to any one of claims 1 to 3, comprising a compound having an allyl group or a methallyl group. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4.

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