JP6452335B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention relates to an epoxy resin composition that provides a cured product excellent in low dielectric properties, high heat resistance, and low moisture absorption, and a cured product thereof.

  In recent years, the signal band of information communication devices such as mobile phones and the CPU clock time of computers have reached the GHz band, and the frequency has been increasing.

  The dielectric loss of an electrical signal is proportional to the product of the square root of the dielectric constant of the insulator forming the circuit, the dielectric loss tangent and the frequency of the signal used. Therefore, the higher the frequency of the signal used, the greater the dielectric loss.

  Dielectric loss attenuates the electrical signal and impairs the reliability of the signal. Therefore, in order to suppress this, it is necessary to select a material having a small dielectric constant and dielectric loss tangent for the insulator (Patent Document 1).

  A material for providing a thermosetting resin composition having such characteristics and a technique using an active ester compound obtained by arylesterifying a phenolic hydroxyl group in a phenol novolak resin as a curing agent for an epoxy resin are known. However, the heat resistance was not sufficient (Patent Documents 2 and 3).

JP 2012-221968 A JP-A-11-130939 JP 7-82348 A

  Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition having a performance excellent in low dielectric property and high heat resistance, and useful for lamination, molding, casting, adhesion and the like, and a cured product thereof. It is to provide.

That is, the present invention
An epoxy resin composition containing an epoxy resin (A) having an epoxy equivalent represented by the following general formula (1) of 2000 g / eq or less and a curing agent (B).

（式中、ｍは繰り返し数で、平均値は０＜ｍ＜５であり、ｎは繰り返し数で、平均値は０≦ｎ＜３であり、Ｘはそれぞれ独立して、ナフチレン基、置換基として炭素数１〜１０の炭化水素基もしくはハロゲン原子を有するナフチレン基、または下記一般式（２）で表される基のいずれかであり、Ｙはそれぞれ独立して、フェニレン基、ナフチレン基、置換基として炭素数１〜１０の炭化水素基もしくはハロゲン原子を有するフェニレン基、置換基として炭素数１〜１０の炭化水素基もしくはハロゲン原子を有するナフチレン基、または下記一般式（２）で表される基のいずれかであり、Ｇはグリシジル基である。）

(In the formula, m is the number of repetitions, the average value is 0 <m < 5 , n is the number of repetitions, the average value is 0 ≦ n < 3 , and X is independently a naphthylene group or a substituent. As a hydrocarbon group having 1 to 10 carbon atoms or a naphthylene group having a halogen atom, or a group represented by the following general formula (2), and each Y is independently a phenylene group, a naphthylene group, or a substituent. A phenylene group having 1 to 10 carbon atoms or a halogen atom as a group, a naphthylene group having 1 to 10 carbon atoms or a halogen atom as a substituent, or the following general formula (2) Any of the groups, and G is a glycidyl group.)

（式中、Ｒ_１はそれぞれ独立して、水素原子、炭素数１〜１０の炭化水素基、またはハロゲン原子のいずれかであり、Ｒ_２は単結合または二価の基である。）

(In the formula, each R ₁ is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and R ₂ is a single bond or a divalent group.)

The epoxy resin (A) is a halogenated methyl group-containing compound (b) 0 represented by the following general formula (4) with respect to 1 mol of the dihydroxy compound (a) represented by the following general formula (3). An epoxy resin obtained by reacting 0.001 to 1.0 mol to obtain a dihydroxy compound (c) represented by the following general formula (5) and then reacting the dihydroxy compound (c) with epichlorohydrin. Preferably there is.

（式中、Ｙは前記一般式（１）のＹと同義である。）

(In the formula, Y has the same meaning as Y in formula (1)).

（式中、Ｘは前記一般式（１）のＸと同義であり、Ｚはハロゲン原子を示す。）

(In the formula, X has the same meaning as X in formula (1), and Z represents a halogen atom.)

（式中、ｍ，Ｘ，Ｙは前記一般式（１）のｍ，Ｘ，Ｙとそれぞれ同義である。）

(In the formula, m, X, and Y are respectively synonymous with m, X, and Y in the general formula (1).)

Moreover, it is preferable that the active hydrogen group of the said hardening | curing agent (B) is 0.4-1.2 mol in the said epoxy resin composition with respect to 1 mol of epoxy groups of the said epoxy resin (A).

  Moreover, this invention is a prepreg obtained from the said epoxy resin composition, an adhesive sheet, an epoxy resin laminated board, an epoxy resin sealing material, or an epoxy resin casting material. Moreover, this invention is a hardened | cured material obtained by hardening | curing the said epoxy resin composition.

The epoxy resin composition of the present invention gives a cured product excellent in low dielectric property and high heat resistance, and can be suitably used for applications such as lamination, molding, casting and adhesion.

The epoxy resin composition of the present invention comprises the epoxy resin (A) represented by the general formula (1) and the curing agent (B) as essential components.

  In the epoxy resin (A) represented by the general formula (1), m is the number of repetitions, and the average value needs to satisfy 0 <m <10, and preferably 0.01 <m <8. Yes, more preferably 0.05 <m <5. When m is 0, the amount of hydroxyl groups is not sufficiently reduced, and the low dielectric properties are not effective. When m is 10 or more, the viscosity may be high. N is the number of repetitions, and the average value must be 0 ≦ n <10, preferably 0 ≦ n <5, more preferably 0 ≦ n <4, and still more preferably 0. ≦ n <3. If n is 10 or more, there is a risk of high viscosity. The epoxy equivalent is not particularly specified, but is 2000 g / eq. The following is preferable, and 1000 g / eq. The following is more preferable. Epoxy equivalent is 2000 g / eq. If it is larger, the molecular weight becomes large, so that there is a risk of high viscosity. Here, the average value is a number average.

Moreover, X of the said General formula (1) is respectively independently represented by the naphthylene group, the C1-C10 hydrocarbon group or naphthylene group which has a halogen atom as a substituent, or the said General formula (2). One of the groups. Y each independently has a phenylene group, a naphthylene group, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent, and a hydrocarbon group or halogen atom having 1 to 10 carbon atoms as a substituent. It is either a naphthylene group or a group represented by the general formula (2). As specific examples of the hydrocarbon group having 1 to 10 carbon atoms as a substituent are the same as those of R ₁ in the general formula (2) to be described later.

In the general formula (2), each R ₁ is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom. Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n A linear or branched alkyl group having 1 to 10 carbon atoms such as a pentyl group or an n-hexyl group, a cyclic alkyl group having 4 to 10 carbon atoms such as a cyclohexyl group, a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. An aryl group optionally having a substituent having 6 to 10 carbon atoms such as an indanyl group, a benzyl group, a phenethyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, 2, Preferred examples include substituents such as 6-dimethylbenzyl group, 3,5-dimethylbenzyl group and α-methylbenzyl group, which may have 7 to 10 carbon atoms, and an aralkyl group. Substituents are methyl, ethyl, tert- butyl group, a cyclohexyl group, a phenyl group, a α- methylbenzyl group.

In the general formula (2), R ₂ is a single bond or a divalent group, and may contain a hetero atom such as a halogen atom, a sulfur atom, a nitrogen atom, or an oxygen atom. Specific examples of the divalent group include —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, —C (CF ₃ ) ₂ —, —CO—, —COO—. , —O—, —S—, —SO ₂ —, benzylidene group, α-methylbenzylidene group, cyclohexylidene group, cyclopentylidene group, 9H-fluorene-9-ylidene group, or cyclohexenyl group. The aromatic skeleton of these groups may further have a substituent having the same meaning as R ₁ . Preferred divalent groups include —CH ₂ —, —C (CH ₃ ) ₂ —, —CO—, —COO—, —O—, —S—, —SO ₂ —, 9H-fluorene-9-ylidene. It is a group.

In the general formulas (1) to (5), the same symbols have the same meanings unless otherwise specified.

The epoxy resin (A) is obtained by first reacting the dihydroxy compound (a) with the halogenated methyl group-containing compound (b) to obtain the dihydroxy compound (c), and then the dihydroxy compound (c) and epichlorohydrin. To obtain a glycidyl etherified hydroxyl group. In the reaction, a small amount of a component having a structure in which an epoxy group is ring-opened and polymerized may be produced, but such a component may be mixed.

Conventionally, it has been known to synthesize a polyether by reacting a hydroxyl group with an alkali metal salt and a halide. The dihydroxy compound (a) and the halogenated methyl group-containing compound (b) for obtaining the hydroxy compound (c) are known. This polyether synthesis method can be used in the reaction with (A). Note that m in the general formulas (1) and (5) is synonymous, but m can be roughly calculated from the molar ratio of the dihydroxy compound (a) and the halogenated methyl group-containing compound (b). As the molar ratio is closer to 1, m increases. However, the ratio (a) / (b) is greater than 1 because both ends need to be hydroxy groups.

Specific examples of the dihydroxy compound (a) include phenylene group-containing dihydroxy compounds such as hydroquinone, resorcin, and catechol, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2, Naphthalenediols such as 7-dihydroxynaphthalene, bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, 4,4′-oxybisphenol, 4,4′-carbonylbisphenol, bisphenolfluorene, Divalent phenols such as 4,4′-biphenol, 2,2′-biphenol, bisphenolacetophenone, 4-hydroxyphenyl-4-hydroxyphenyl, and the like Wherein the R ₁ as defined in (2), etc. These compounds having as a substituent a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms. Preferably, 4-hexyl resorcinol, 2,5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, 1,6-dihydroxynaphthalene, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethyl Biphenol, 4,4′-oxybisphenol, 4,4′-carbonylbisphenol, bisphenol fluorene, and tetrabromobisphenol A are preferable, and tetramethylbisphenol S, bisphenol fluorene, and tetrabromobisphenol A are more preferable.

Specific examples of the halogenated methyl group-containing compound (b) include bischloromethylnaphthalene, bischloromethylbiphenyl, bisbromomethylbiphenyl, bischloromethylfluorene, and the like, and R in the general formula (2) ₁ synonymous, etc. these compounds having a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms.

In order to obtain the dihydroxy compound (c) suitable for the epoxy resin (A), how to combine the dihydroxy compound (a) exemplified above and the halogenated methyl group-containing compound (b) exemplified above However, more preferable combinations of the dihydroxy compound (a) and the halogenated methyl group-containing compound (b) are bischloromethylnaphthalene and tetramethylbisphenol S, bischloromethylnaphthalene and tetramethylbiphenol, bischloro. Methylnaphthalene and dihydroxynaphthalene, bischloromethylnaphthalene and bisphenol A, bischloromethylnaphthalene and tetramethylbisphenol A, bischloromethylnaphthalene and tetramethylbisphenol F, bischloromethylnaphthalene and 2,5-di-te t-butylhydroquinone, bischloromethylnaphthalene and bisphenol F having an α-methylbenzyl group as a substituent, bischloromethylbiphenyl and tetramethylbisphenol S, bischloromethylbiphenyl and tetramethylbiphenol, bischloromethylbiphenyl and dihydroxynaphthalene, Bischloromethylbiphenyl and bisphenol A, bischloromethylbiphenyl and tetramethylbisphenol A, bischloromethylbiphenyl and tetramethylbisphenol F, bischloromethylbiphenyl and 2,5-di-tert-butylhydroquinone, and bischloromethylbiphenyl Bisphenol F having an α-methylbenzyl group as a substituent, bisbromomethylbiphenyl, tetramethylbisphenol F, bischlorome Rufuruoren and tetramethyl bisphenol F or the like is go up. Among these, more preferred combinations include bischloromethylnaphthalene and tetramethylbisphenol S, bischloromethylbiphenyl and tetramethylbisphenol S, bischloromethylbiphenyl and tetramethylbisphenol F, and bischloromethylbiphenyl and substituents from the viewpoint of adhesiveness. Bisphenol F having an α-methylbenzyl group as bischloromethylnaphthalene and tetramethylbisphenol S, bischloromethylnaphthalene and dihydroxynaphthalene, bischloromethylnaphthalene and 2,5-di-tert-butylhydroquinone from the viewpoint of heat resistance Bischloromethylbiphenyl and tetramethylbisphenol S, bischloromethylbiphenyl and tetramethylbiphenol, bischloromethylbiphenyl and tetramethyl Bisphenol F and the like.

Moreover, in order to obtain the said dihydroxy compound (c) suitable for the said epoxy resin (A), the said halogenated methyl group containing compound (b) is 0.001 with respect to 1.0 mol of said dihydroxy compounds (a). It is necessary to make it react in the range of -1.0 mol, a preferable range is 0.01-0.9 mol, a more preferable range is 0.05-0.8 mol, and a still more preferable range is 0. .1 to 0.7 mol. When the halogenated methyl group-containing compound (b) exceeds 1 mol, the end group of the dihydroxy compound (c) becomes halogen, so that the epoxy resin (A) represented by the general formula (1) is obtained. Absent.

  The reaction between the dihydroxy compound (a) and the halogenated methyl group-containing compound (b) can be carried out in the presence of an alkali metal hydroxide such as potassium carbonate, sodium hydroxide, potassium hydroxide, etc. 1.8-2.5 mol is preferable with respect to 1.0 mol of said dihydroxy compounds (a), and, as for the usage-amount of an oxide, 2.0-2.2 mol is more preferable. Moreover, reaction temperature is 20-100 degreeC, Preferably it is 40-80 degreeC, More preferably, it is 50-60 degreeC. The reaction time is 1 to 10 hours, preferably 2 to 5 hours. The reaction does not proceed at 20 ° C. or lower, and an electrophilic substitution reaction may occur as a side reaction at 100 ° C. or higher.

The epoxy resin (A) can be obtained by further reacting the dihydroxy compound (c) obtained by reacting the dihydroxy compound (a) and the halogenated methyl group-containing compound (b) with epichlorohydrin. it can. For example, after the dihydroxy compound (c) is dissolved in excess epichlorohydrin, it is in the range of 20 to 150 ° C., preferably 30 to 80 ° C. in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. For 1 to 10 hours, and after the epoxidation reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then The target epoxy resin (A) can be obtained by distilling off the solvent.

The amount of the alkali metal hydroxide used at this time is 0.8 to 2.5 mol, preferably 0.85 to 2.0 mol, more preferably relative to 1 mol of the hydroxyl group of the dihydroxy compound (c). The range is 0.9 to 1.5 mol.

Moreover, the usage-amount of epichlorohydrin is used excessively with respect to the hydroxyl group in the said dihydroxy compound (c), and is 1.5-15 mol normally with respect to 1 mol of hydroxyl groups, Preferably it is the range of 2-10 mol. .

As a more preferable method for obtaining the epoxy resin (A), the dihydroxy compound (a) and the halogenated methyl group-containing compound (b) are reacted and then subjected to a neutralization step as the dihydroxy compound (c). There is a method of reacting with epichlorohydrin immediately without taking it out. In this method, the alkali metal hydroxide remaining in the reaction between the dihydroxy compound (a) and the halogenated methyl group-containing compound (b) is also considered as an alkali metal hydroxide used for the epoxidation reaction.

In addition, the average value of n of the said General formula (1) can be calculated | required by calculation from the epoxy equivalent of the said epoxy resin (A).

  As said hardening | curing agent (B) used for the epoxy resin composition of this invention, normally used hardening | curing agent for epoxy resins, such as various phenol resins, acid anhydrides, amines, hydrazides, and active esters, is used. These curing agents may be used alone or in combination of two or more. Further, for lowering the dielectric loss tangent, a curing agent having a lower functional group concentration after curing is preferable, and a high hydroxyl equivalent phenol resin and active esters are preferable.

Specific examples of the phenol resins include tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolak, naphthol novolak, Trivalent or higher phenolic compounds represented by dicyclopentadiene type phenol resin, phenol aralkyl resin and the like, and also phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol , 2,2'-biphenol, hydroquinone, resorcin, catechol, naphthalene diol and the like, and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylyl Polyphenol compounds synthesized by reaction with cross-linking agents such as diglycol, p-xylylene glycol dimethyl ether, divinylbenzene, diisopropenylbenzene, dimethoxymethylbiphenyls, divinylbiphenyl, diisopropenylbiphenyls, and phenols Examples thereof include biphenyl aralkyl type phenol resins obtained from bischloromethylbiphenyl and the like, naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride and the like.

Specific examples of the acid anhydrides include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, methylnadic acid anhydride, benzophenonetetracarboxylic dianhydride Products, biphenyltetracarboxylic dianhydride and the like.

Specific examples of the amines include condensates of acids such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, dicyandiamide, and dimer acid with polyamines. Examples include amine compounds such as polyamide amine.

Specific examples of the hydrazides include adipic acid hydrazide, sepatin hydrazide, isophthalic acid hydrazide, and the like.

Specific examples of the active esters include EPICLON HPC-8000-65T (manufactured by DIC Corporation).

In the epoxy resin composition of the present invention, the active hydrogen group of the curing agent (B) is preferably in the range of 0.4 to 1.2 mol with respect to 1 mol of the epoxy group of the epoxy resin (A). 5-1.1 mol is more preferable and 0.7-1.0 mol is still more preferable.

  A curing accelerator can be used in the epoxy resin composition of the present invention as necessary. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diaza. -Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine and triphenylphosphine triphenylborane, and metal compounds such as tin octylate. These curing accelerators may be used alone or in combination of two or more. As for these hardening accelerators, 0.02-5.0 mass parts is used as needed with respect to 100 mass parts of said epoxy resins (A) in the epoxy resin composition of this invention. By using these curing accelerators, the curing temperature can be lowered or the curing time can be shortened.

  In the epoxy resin composition of the present invention, the epoxy resin (A) represented by the general formula (1) is an essential epoxy resin as an epoxy resin component, but other epoxy is used as long as the object of the present invention is not impaired. A resin can also be used in combination.

  Specific examples of other epoxy resins that can be used in combination include bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene, 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4 ′. -Epoxidized products of divalent phenols such as dihydroxybiphenyl, resorcin, naphthalenediols, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, Epoxides of tri- or higher valent phenols such as o-cresol novolak, epoxidized products of co-condensation resins obtained from dicyclopentadiene and phenols, epoxies of co-condensation resins obtained from cresols, formaldehyde and alkoxy-substituted naphthalenes Chemicals, phenols and Epoxy products of phenol aralkyl resins obtained from xylylene dichloride, epoxidized products of biphenyl aralkyl type phenol resins obtained from phenols and bischloromethylbiphenyl, naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride, etc. And epoxidized products thereof. These epoxy resins may be used alone or in combination of two or more. These blending amounts may be in a range that does not impair the object of the present invention, but are preferably 50 with respect to the total of the epoxy resin (A) represented by the general formula (1) and other epoxy resins. It is less than mass%, more preferably less than 40 mass%, still more preferably less than 25 mass%.

  In the epoxy resin composition of the present invention, an organic solvent can also be used for viscosity adjustment. Specific examples of organic solvents that can be used include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, Aromatic hydrocarbons such as benzene and toluene are exemplified. These organic solvents may be used alone or in combination of two or more.

  The epoxy resin composition of the present invention may be blended with a curable resin or a thermoplastic resin other than the epoxy resin as long as the characteristics are not impaired. Specifically, phenol resin, acrylic resin, petroleum resin, indene resin, indene coumarone resin, phenoxy resin, cyanate resin, epoxy acrylate resin, vinyl compound, polyurethane, polyester, polyamide, polyimide, polyamideimide, polyether Examples thereof include, but are not limited to, imide, bismaleimide triazine resin, polyethersulfone, polysulfone, polyetheretherketone, polyphenylene sulfide, and polyvinyl formal.

  A filler can be used for the epoxy resin composition of this invention as needed. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium hydroxide, glass powder, silica balloon, etc., but organic or inorganic moisture-resistant pigments In addition, pigments such as scaly pigments may be blended. The reason for using a general inorganic filler is an improvement in impact resistance. Moreover, fibrous fillers, such as glass fiber, a pulp fiber, a synthetic fiber, a ceramic fiber, organic fillers, such as fine particle rubber and a thermoplastic elastomer, etc. can be mix | blended.

  Moreover, you may mix | blend additives, such as a flame retardant, a thixotropic agent, and a fluidity improver, in the epoxy resin composition of this invention as needed. Examples of the thixotropic agent include silicon, castor oil, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite. Further, if necessary, the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a colorant such as carbon black, a flame retardant such as antimony trioxide, a low stress agent such as silicon oil, A lubricant such as calcium stearate can be blended.

  Next, the prepreg obtained by using the epoxy resin composition of the present invention will be described. As the sheet-like substrate, inorganic fibers such as glass, or woven or non-woven fabrics of organic fibers such as polyester, polyamine, polyacryl, polyimide, Kevlar, etc. can be used, but it is not limited thereto. The method for producing the prepreg from the epoxy resin composition and the substrate of the present invention is not particularly limited. For example, the sheet-like substrate is immersed in a resin varnish whose viscosity is adjusted with a solvent of the epoxy resin composition. After impregnation, the resin component is obtained by drying by heating and semi-curing (B-stage). For example, it can be dried by heating at 100 to 200 ° C. for 1 to 40 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80% by mass.

  Next, an adhesive sheet obtained using the epoxy resin composition of the present invention will be described. Although it does not specifically limit as a method to manufacture an adhesive sheet, For example, on the carrier film which does not melt | dissolve in epoxy resin compositions, such as a polyester film and a polyimide film, Preferably the epoxy resin composition of this invention is 5-100 micrometers. After being applied to the thickness of the film, it is dried by heating at 100 to 200 ° C. for 1 to 40 minutes to form a sheet. A resin sheet is generally formed by a method called a casting method. At this time, if the sheet to which the epoxy resin composition is applied is previously surface-treated with a release agent, the molded adhesive sheet can be easily peeled off. Here, the thickness of the adhesive sheet is preferably 5 to 80 μm. The adhesive sheet thus obtained usually becomes an insulating adhesive sheet having insulation, but the conductive adhesive sheet is obtained by mixing conductive metal or metal-coated fine particles with the epoxy resin composition. Can be obtained.

Next, a method for producing a laminate using the prepreg or insulating adhesive sheet of the present invention will be described. When forming a laminated board using prepreg, one or more prepregs are laminated, a metal foil is placed on one or both sides to form a laminate, and this laminate is heated and pressed to integrate the laminate. To do. Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel or the like can be used. Conditions for heating and pressurizing the laminate may be adjusted as appropriate under the conditions for curing the epoxy resin composition, and heating and pressurizing. However, if the amount of pressurization is too low, bubbles are generated inside the resulting laminate. Since it may remain and electrical characteristics may deteriorate, it is desirable to apply pressure under conditions that satisfy moldability. For example, the temperature can be set to 160 to 220 ° C., the pressure can be set to 0.49 to 4.9 MPa (5 to 50 kgf / cm ² ), and the heating time can be set to 40 to 240 minutes. Furthermore, a multilayer board can be produced using the single-layer laminated board thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution to perform a blackening process to obtain an inner layer material. An insulating layer is formed by prepreg or an insulating adhesive sheet on one or both sides of the circuit forming surface of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board. When forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is arrange | positioned on the circuit formation surface of several inner-layer material, and a laminated body is formed. Alternatively, an insulating adhesive sheet is disposed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressed to be integrally molded, thereby forming a cured product of the insulating adhesive sheet as an insulating layer, and forming a multilayered inner layer material. Alternatively, the inner layer material and the metal foil as the conductor layer are formed by using the cured product of the insulating adhesive sheet as the insulating layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer material can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. When an insulating layer is formed by applying an epoxy resin composition to a laminate, the outermost circuit-forming surface resin of the inner layer material is preferably applied to the epoxy resin composition to a thickness of 5 to 100 μm, and then 100 to 100- It is heated and dried at 200 ° C. for 1 to 90 minutes to form a sheet. It is generally formed by a method called a casting method. The thickness after drying is preferably 5 to 80 μm. A printed wiring board can be formed by further forming a via hole or a circuit by the additive method or the subtractive method on the surface of the multilayer laminate thus formed. Further, by repeating the above method using this printed wiring board as an inner layer material, a multilayer laminate can be formed. When an insulating layer is formed with a prepreg, a laminate is formed by placing one or a plurality of laminated prepregs on the circuit forming surface of the inner layer material, and further placing a metal foil on the outside thereof. . Then, this laminate is heated and pressed to be integrally formed, whereby a cured product of the prepreg is formed as an insulating layer, and the outer metal foil is formed as a conductor layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer board can also be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. A printed wiring board can be molded by further forming via holes or circuits by the additive method or the subtractive method on the surface of the multilayer laminate thus formed. Further, by repeating the above method using the printed wiring board as an inner layer material, a multilayer board can be formed.

  Moreover, if the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be obtained, and this cured product is excellent in terms of low dielectric properties, heat resistance, low hygroscopicity, and the like. Moreover, this hardened | cured material can be obtained by shape | molding an epoxy resin composition by methods, such as casting, compression formation, and transfer formation. The temperature at this time is usually in the range of 120 to 250 ° C.

  The epoxy resin composition of the present invention and the prepreg, adhesive sheet, laminate, sealant, cast product, and cured product obtained using the composition have excellent low dielectric properties, heat resistance, and low hygroscopicity. In addition, the material exhibited excellent adhesive properties.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to this. In Examples, unless otherwise specified, “part” represents part by mass, and “%” represents mass%. In the present invention, the following test method was used.

(1) Measurement of epoxy equivalent It measured based on JISK7236 specification. Specifically, a potentiometric titrator was used, methyl ethyl ketone was used as a solvent, a brominated tetraethylammonium acetic acid solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was used.

(2) Measurement of softening point Measured according to JIS K 7234 standard and ring and ball method. Specifically, an automatic softening point apparatus (manufactured by Meitec Co., Ltd., ASP-MG4) was used.

(3) Measurement of glass transition temperature It measured based on JISK7121, differential scanning calorimetry. Using an EXTER DSC6200 manufactured by SII, the temperature was measured at a rate of temperature increase from 20 ° C. to 10 ° C./min, and obtained from the extrapolated glass transition start temperature (Tig) of the DSC chart obtained in the second cycle.

(4) Measurement of relative permittivity and dielectric loss tangent 1 GHz by cavity resonance method (vector network analyzer (VNA) E8363B (manufactured by Agilent Technologies), cavity resonator perturbation method permittivity measurement device (manufactured by Kanto Electronics Co., Ltd.)) The value was measured.

(5) Measurement of adhesive strength In accordance with JIS K 6854-1, an autograph manufactured by Shimadzu Corporation under an atmosphere of 25 ° C. and 50 mm / min. It was measured by.

(6) Measurement of water resistance Solder heat resistance after PCT was measured as an index of water resistance. A test piece prepared according to JIS C 6481 was treated in an autoclave at 121 ° C. and 0.2 MPa for 3 hours, then placed in a 260 ° C. solder bath, and no swelling or peeling occurred for 20 minutes or more. The case where swelling or peeling occurred within 10 minutes was evaluated as x, and the others were evaluated as Δ.

(7) Tensile strength According to JIS K 7113.

Synthesis Example 1 (Synthesis of epoxy resin (A1))
A four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device was charged with 806 parts of methanol and 201.5 parts of potassium hydroxide, and the dihydroxy compound ( As a), 550 parts of bis (4-hydroxy-3,5-dimethylphenyl) sulfone (hereinafter abbreviated as TMBPS) was added to obtain an alkali metal salt. Thereafter, 4.5 parts of 4,4′-bischloromethylbiphenyl (hereinafter abbreviated as BCMB) as the halogenated methyl group-containing compound (b) and bis (2-methoxyethyl) ether (hereinafter abbreviated as DEDM) as the solvent. ) Was charged, and the temperature was raised to 75 ° C. while stirring and reacted for 2 hours. After completion of the reaction, the temperature was raised to 100 ° C. under a reduced pressure of 0.0067 MPa (50 mmHg), and after distilling out the total amount of methanol, 1644 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, 148 parts of 48% aqueous sodium hydroxide solution was added dropwise over 2 hours under a reduced pressure of 0.024 MPa (180 mmHg), and the refluxed water and epichlorohydrin were added in a separate layer. After separation, epichlorohydrin was returned to the reaction vessel, and water was removed from the system to react. After completion of the dropwise addition, the reaction was continued for an additional hour under the same conditions. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 600 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin is 212 g / eq. The softening point was 60 ° C.

Synthesis Example 2 (Synthesis of epoxy resin (A2))
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device was charged with 366 parts of methanol and 91.6 parts of potassium hydroxide, and the dihydroxy compound ( As a), 125 parts of TMBPS and 90 parts of 4,4′-dihydroxydiphenylsulfone were added to obtain an alkali metal salt. Thereafter, 61.5 parts of BCMB as the halogenated methyl group-containing compound (b) and 360 parts of DEDM as the solvent were added, the temperature was raised to 75 ° C. with stirring, and the reaction was performed for 2 hours. After completion of the reaction, the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg, and after methanol and 43 parts of DEDM were distilled off, 528 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining at 75 ° C. under a reduced pressure of 180 mmHg, 48 parts of 48% aqueous sodium hydroxide solution is added dropwise over 1 hour, and water and epichlorohydrin distilled off during the addition are separated in a separation layer, and epichlorohydrin is reacted. It returned to the container and water was removed out of the system and reacted. After completion of the dropwise addition, the reaction was continued for an additional hour under the same conditions. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 253 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin is 313 g / eq. The softening point was 92 ° C.

Synthesis Example 3 (Synthesis of epoxy resin (A3))
A four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device was charged with 293 parts of methanol and 73.3 parts of potassium hydroxide. As a), 200 parts of TMBPS was added to obtain an alkali metal salt. Thereafter, 114.8 parts of BCMB as the halogenated methyl group-containing compound (b) and 440 parts of DEDM as the solvent were added, and the temperature was raised to 75 ° C. with stirring, followed by reaction for 2 hours. After completion of the reaction, the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg. After distilling out the total amount of methanol and 333 parts of DEDM, 182 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining at 75 ° C. under a reduced pressure of 180 mmHg, 10 parts of a 48% aqueous sodium hydroxide solution is added dropwise over 30 minutes, and water and epichlorohydrin distilled under reflux are separated in a separation layer, and epichlorohydrin is reacted. It returned to the container and water was removed out of the system and reacted. After completion of the dropwise addition, the reaction was continued for 90 minutes under the same conditions. After completion of the reaction, the salt produced by filtration was removed, and epichlorohydrin was distilled off to obtain 247 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin was 776 g / eq. The softening point was 135 ° C.

Synthesis Example 4 (Synthesis of epoxy resin (A4))
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device was charged with 366 parts of methanol and 99 parts of potassium hydroxide, and the dihydroxy compound (a) was stirred into the flask. As an alkali metal salt, 250 parts of 4,4′-methylenebis (2,6-dimethylphenol) (hereinafter abbreviated as TMBPF) was added. Thereafter, 122.5 parts of BCMB as the halogenated methyl group-containing compound (b) and 265 parts of DEDM as the solvent were added, the temperature was raised to 75 ° C. with stirring, and the reaction was performed for 2 hours. After completion of the reaction, the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg, and after all the methanol was distilled off, 632 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining at 75 ° C. under a reduced pressure of 180 mmHg, 27 parts of a 48% aqueous sodium hydroxide solution are added dropwise over 1 hour, and water and epichlorohydrin distilled off during the addition are separated in a separation layer, and epichlorohydrin is reacted. It returned to the container and water was removed out of the system and reacted. After completion of the dropwise addition, the reaction was continued for an additional hour under the same conditions. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 285 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin is 454 g / eq. The softening point was 67 ° C.

Synthesis Example 5 (Synthesis of epoxy resin (A5))
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introducing device, 256 parts of methanol and 676 parts of potassium hydroxide were charged, and the dihydroxy compound (a) was stirred. As an alkali metal salt, 200 parts of 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter abbreviated as BPFL) was added. Thereafter, 71.7 parts of BCMB as the halogenated methyl group-containing compound (b) and 378 parts of DEDM as the solvent were added, the temperature was raised to 75 ° C. with stirring, and the reaction was performed for 2 hours. After completion of the reaction, the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg, and after all the methanol was distilled off, 264 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining at 75 ° C. under a reduced pressure of 180 mmHg, 25 parts of 48% aqueous sodium hydroxide solution is added dropwise over 1 hour, and water and epichlorohydrin distilled under reflux are separated in a separation layer, and epichlorohydrin is reacted. It returned to the container and water was removed out of the system and reacted. After completion of the dropwise addition, the reaction was continued for an additional hour under the same conditions. After completion of the reaction, the salt generated by filtration was removed, and epichlorohydrin was distilled off to obtain 226 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin was 497 g / eq. The softening point was 147 ° C.

Synthesis Example 6 (Synthesis of epoxy resin (A6))
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device was charged with 185 parts of methanol and 62 parts of potassium hydroxide, and the dihydroxy compound (a) was stirred. As an alkali metal salt, 125 parts of TMBPF was added. Then, 55 parts BCMN (mixture of 1,4-bis (chloromethyl) naphthalene and 1,5-bis (chloromethyl) naphthalene) as a halogenated methyl group-containing compound (b) and 220 parts DEDM as a solvent were added. While stirring, the temperature was raised to 75 ° C. and reacted for 4 hours. After completion of the reaction, the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg, and after distilling off the total amount of methanol and 180 parts of DEDM, 310 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining at 75 ° C. under a reduced pressure of 180 mmHg, 29 parts of 48% aqueous sodium hydroxide solution is added dropwise over 1 hour, and water and epichlorohydrin distilled under reflux are separated in a separation layer, and epichlorohydrin is reacted. It returned to the container and water was removed out of the system and reacted. After completion of the dropwise addition, the reaction was continued for an additional hour under the same conditions. After completion of the reaction, the salt formed by filtration was removed, and epichlorohydrin was distilled off to obtain 115 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin is 396 g / eq. The softening point was 71 ° C.

Synthesis Example 7 (Synthesis of epoxy resin (A7))
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device was charged with 366 parts of methanol and 91.6 parts of potassium hydroxide, and the dihydroxy compound ( As a), 182 parts of 2,5-di-tert-butylhydroquinone (hereinafter abbreviated as DBHQ) was added to obtain an alkali metal salt. Thereafter, 61.7 parts of BCMB as the halogenated methyl group-containing compound (b) and 360 parts of DEDM as the solvent were added, the temperature was raised to 75 ° C. with stirring, and the reaction was performed for 2 hours. After completion of the reaction, the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg, and after methanol and 43 parts of DEDM were distilled off, 528 parts of epichlorohydrin was added and dissolved by stirring. After uniformly dissolving, maintaining at 75 ° C. under a reduced pressure of 180 mmHg, 48 parts of 48% aqueous sodium hydroxide solution is added dropwise over 1 hour, and water and epichlorohydrin distilled off during the addition are separated in a separation layer, and epichlorohydrin is reacted. It returned to the container and water was removed out of the system and reacted. After completion of the dropwise addition, the reaction was continued for an additional hour under the same conditions. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 286 parts of a pale yellow solid epoxy resin. The epoxy equivalent of the obtained epoxy resin is 270 g / eq. The softening point was 104 ° C.

Epoxy resins, curing agents, and curing accelerators used in Examples and Comparative Examples are as follows.

Epoxy resin (A)
(A1): Epoxy resin of Synthesis Example 1 (A2): Epoxy resin of Synthesis Example 2 (A3): Epoxy resin of Synthesis Example 3 (A4): Epoxy resin of Synthesis Example 4 (A5): Epoxy resin of Synthesis Example 5 (A6): Epoxy resin of Synthesis Example 6 (A7): Epoxy resin of Synthesis Example 7 (A8): TX-0902 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., reaction product of TMBPS and epichlorohydrin, epoxy equivalent = 212 g / eq. , Softening point = 56 ° C)
(A9): Epototo YD-011 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type solid epoxy resin, epoxy equivalent = 475 g / eq., Softening point = 68 ° C.)
(A10): Epototo YD-903N (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type solid epoxy resin, epoxy equivalent = 812 g / eq., Softening point = 96 ° C.)
(A11): Epototo YDC-1312 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., reaction product of DBHQ and epichlorohydrin, epoxy equivalent = 178 g / eq., Melting point = 142 ° C.)

Curing agent (B)
(B1): Shonor BRG-557 (manufactured by Showa Denko KK, phenol novolac resin, phenolic hydroxyl group equivalent = 105 g / eq., Softening point = 86 ° C.)
(B2): Dicyandiamide (DICY, active hydrogen equivalent = 21 g / eq.)
(B3): Ricacid MH-700 (manufactured by Shin Nippon Rika Co., Ltd., a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, active hydrogen equivalent = 164 g / eq.)
(B4): Kayahard AA (manufactured by Nippon Kayaku Co., Ltd., diethyldiaminodiphenylmethane, active hydrogen equivalent = 63 g / eq., Viscosity = 2500 mPa · s)

Curing accelerator (C1): 2E4MZ (manufactured by Shikoku Kasei Co., Ltd., 2-ethyl-4-methylimidazole)
(C2): DCMU (Hodogaya Chemical Co., Ltd., 3,4-dichlorophenyl-1,1-dimethylurea)

Examples 1-5 and Comparative Examples 1-2
An epoxy resin (A), a curing agent (B), a curing accelerator, and a solvent were blended according to the formulation shown in Table 1 to obtain an epoxy resin composition varnish having a nonvolatile content of 50%. The epoxy resin (A), the curing agent (B), and the curing accelerator were used by dissolving in advance in methyl ethyl ketone (MEK). After impregnating the obtained epoxy resin composition varnish into a glass cloth (Nittobo Co., Ltd., IPC standard 2116), the impregnated cloth was dried in a hot air circulating oven at 150 ° C. for 8 minutes, and B stage A prepreg was obtained. Furthermore, 4 sheets of the obtained prepreg and copper foil (Mitsui Metal Mining Co., Ltd., 3EC-III, thickness 35 μm) are stacked, and a vacuum press of 2 MPa is performed at a temperature condition of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes, A double-sided copper-clad laminate with a thickness of 0.5 mm was obtained. Using the obtained double-sided copper-clad laminate, glass transition temperature, adhesive strength, and water resistance were evaluated. Also, the B-stage resin composition is separated from the glass cloth of the B-stage prepreg and vacuum-pressed at 2 MPa under a temperature condition of 190 ° C. × 80 minutes to obtain a cured product for evaluation of relative dielectric constant and dielectric loss tangent. Obtained. The evaluation results are shown in Table 1.

Examples 6-9 and Comparative Examples 3-5
An epoxy resin (A), a curing agent (B), and a curing accelerator were blended according to the blending formulation shown in Table 2, and the mixture was heated and mixed in a heating kneader to obtain a resin composition. Next, after aligning high-strength carbon fibers (Toray Industries, Inc., T700, tensile strength 4.8 GPa, tensile modulus 235 GPa) in one direction, the obtained resin composition is heated and melted, and pressure is applied. Impregnation was performed to obtain a unidirectional carbon fiber prepreg having a resin content of 35%. The obtained prepreg was cut into a length of 30 cm and a width of 30 cm to form a laminate by laminating 17 sheets so that the fiber directions would be the same, and after overlapping the release cloth, the bleeder cloth was laminated, and further the bleeder cloth And wrapped with a nylon pack to form a molding stack. This forming stack was autoclaved at 130 ° C. for 1 hour to obtain a carbon fiber composite material having a fiber volume content of 60%. Using the obtained carbon fiber composite material, glass transition temperature, bending strength, and bending elastic modulus were evaluated. In addition, the measurement method of the resin content rate in a prepreg was measured according to JISK7071, and the fiber volume content rate was measured according to JISH7401. Further, the resin composition that was heated and mixed in a heating kneader was vacuum-pressed at 2 MPa under a temperature condition of 190 ° C. × 80 minutes to obtain a cured product for evaluation of relative dielectric constant and dielectric loss tangent. The evaluation results are shown in Table 2.

Examples 10-13 and Comparative Examples 6-8
An epoxy resin (A), a curing agent (B), and a curing accelerator were blended according to the formulation shown in Table 3, and the mixture was stirred and homogenized while heating to 120 ° C. to obtain an epoxy resin composition. The obtained epoxy resin composition was degassed under reduced pressure, then poured into a mold, and cured in a hot air circulating oven at 150 ° C. for 2 hours and then at 180 ° C. for 3 hours, to obtain a cast cured product. Got. The obtained cast cured product was evaluated for glass transition temperature, relative dielectric constant, and dielectric loss tangent. The evaluation results are shown in Table 3.

Claims (9)

The epoxy resin composition containing the epoxy resin (A) and the hardening | curing agent (B) whose epoxy equivalent represented by following General formula (1) is 2000 g / eq or less .

(In the formula, m is the number of repetitions, the average value is 0 <m < 5 , n is the number of repetitions, the average value is 0 ≦ n < 3 , and X is independently a naphthylene group or a substituent. As a hydrocarbon group having 1 to 10 carbon atoms or a naphthylene group having a halogen atom, or a group represented by the following general formula (2), and each Y is independently a phenylene group, a naphthylene group, or a substituent. A phenylene group having 1 to 10 carbon atoms or a halogen atom as a group, a naphthylene group having 1 to 10 carbon atoms or a halogen atom as a substituent, or the following general formula (2) Any of the groups, and G is a glycidyl group.)

(In the formula, each R ₁ is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and R ₂ is a single bond or a divalent group.) The epoxy resin (A) is a halogenated methyl group-containing compound (b) represented by the following general formula (4) with respect to 1 mol of the dihydroxy compound (a) represented by the following general formula (3). The epoxy resin obtained by further reacting the dihydroxy compound (c) represented by the following general formula (5) obtained by reacting in the range of 001 to 1.0 mol with epichlorohydrin. Epoxy resin composition.

(In the formula, Y is a phenylene group, a naphthylene group, a phenylene group having a C 1-10 hydrocarbon group or a halogen atom as a substituent, and a naphthylene having a C 1-10 hydrocarbon group or a halogen atom as a substituent. Either a group or a group represented by the following general formula (2).)

(In the formula, each R ₁ is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and R ₂ is a single bond or a divalent group.)

(Wherein X is a naphthylene group, a hydrocarbon group having 1 to 10 carbon atoms or a naphthylene group having a halogen atom as a substituent, or a group represented by the following general formula (2); Indicates an atom.)

(In the formula, each R ₁ is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and R ₂ is a single bond or a divalent group.)

(In the formula, m is the number of repeats, the average value is 0 <m < 5 , and X is independently a naphthylene group, a naphthylene group having a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent. Or any one of the groups represented by the following general formula (2), and each Y independently represents a phenylene group, a naphthylene group, a phenylene having a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent. A group, a hydrocarbon group having 1 to 10 carbon atoms or a naphthylene group having a halogen atom as a substituent, or a group represented by the following general formula (2).

(In the formula, each R ₁ is independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and R ₂ is a single bond or a divalent group.) The epoxy resin composition according to claim 1, wherein the active hydrogen group of the curing agent (B) is in the range of 0.4 to 1.2 mol with respect to 1 mol of the epoxy group of the epoxy resin (A). A prepreg using the epoxy resin composition according to any one of claims 1 to 3. An adhesive sheet using the epoxy resin composition according to any one of claims 1 to 3. The epoxy resin laminated board characterized by using the epoxy resin composition of any one of Claims 1-3. An epoxy resin sealing material using the epoxy resin composition according to claim 1.   An epoxy resin casting material comprising the epoxy resin composition according to claim 1.   Hardened | cured material which hardened the epoxy resin composition of any one of Claims 1-3.