TWI623562B - Epoxy resin composition and cured product thereof - Google Patents

Abstract

The present invention provides an epoxy resin composition and a cured product thereof which have excellent properties of low dielectric properties and high heat resistance, and can be used for lamination, molding, casting, and adhesion.

The epoxy resin composition and its hardened | cured material of this invention contain the epoxy resin (A) and hardening | curing agent (B) represented by General formula (1).

(In the formula, m is the number of repeating units, and the average value is 0 <m <10. X and Y may also be selected from the group consisting of phenylene and naphthyl, which may be substituted by a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms. Or at least one kind of the group represented by the general formula (2) may be the same or different.)

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

Description

Epoxy resin composition and hardened material thereof

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

In recent years, the demand for small mobile communication devices such as smart phones or tablet personal communication terminals has grown rapidly. With this, the signal bandwidth of the information communication equipment and the computer's CPU frequency have reached the GHZ frequency range, and further higher frequency has been gradually achieved.

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

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

As a representative insulating material used for the above-mentioned communication equipment, epoxy resin can be exemplified. However, for example, even in a printed laminated board, of course, It is required to provide basic properties such as a specific permittivity and a small dielectric loss tangent, and the same heat resistance or adhesiveness as before. Recently, in accordance with the environment, halogen-free flame retardants have been continuously implemented.

Among the halogen-free flame-retardant methods, many reports have proposed the reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with a reactive phosphorus compound with an epoxy group. Method. In order to improve the appearance of flame retardance in this method, it is necessary to increase the phosphorus content rate, which leads to a reduction in the number of epoxy groups contained in one molecule, and problems such as a decrease in the crosslinking density of the hardened material and deterioration in heat resistance remain.

For this problem, it is generally tried to use a polyfunctional epoxy resin and a polyfunctional hardener to improve the crosslinking density. However, by this method, the hardened product becomes brittle and the good adhesion of the epoxy resin is reduced. At the same time, the concentration of hydroxyl groups generated in the hardened material also increases with the curing reaction of the epoxy resin, and there is a significant problem that the dielectric characteristics are deteriorated.

That is, this fact means that there is no material that satisfies the reduction of the electromotive property against the required heat resistance or flame resistance, and the adhesive strength is improved. In the conventional design concepts of epoxy resins and hardeners, It is very difficult to solve this problem.

For such a difficult subject, many reports have proposed a technique for improving the cyanate ester compound in combination with an epoxy resin and a hardener thereof. These materials are effective in improving the dielectric properties, but as the amount of use increases, the hardened material becomes hard, and it is difficult to sufficiently satisfy any of adhesiveness, flame retardancy, and workability (Patent Document 2).

Yet another low dielectric material is a polyphenylene ether resin with phenol Many reports have also been made on the methods of using modified phenol compounds and epoxy resins in combination with compounds. Here, the modified phenol material imparting a low dielectric material has a molecular weight that is necessarily increased as it is decomposed and repolymerized during synthesis, resulting in a decrease in workability when impregnated with glass cloth or the like. The point that raw materials are expensive is also very unfavorable for the development of the use of communication terminals which are becoming more and more widespread (Patent Document 3).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2012-221968

[Patent Document 2] Japanese Unexamined Patent Publication No. 06-248074

[Patent Document 3] Japanese Patent Laid-Open No. 10-273518

Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition and its hardened product which have properties of low dielectric properties and high heat resistance, and which can be used for lamination, molding, casting, and bonding.

That is, the epoxy resin composition of this invention contains an epoxy resin (A) and a phenol compound (B) represented by General formula (1).

(In the formula, m is the number of repeating units, and the average value is 0 <m <10. X and Y are selected from the group consisting of phenylene, naphthyl, or general alkylene, which may have a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms as a substituent. (At least one kind of the base represented by the formula (2) may be the same or different.)

(In the formula, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, which may be the same as or different from each other. R ₂ is a single bond or a divalent group.)

The phenol compound (B) is preferably one mole of the dihydroxy compound (a) represented by the following general formula (3), and the halogenated methyl compound represented by the following general formula (4) is used. (b) The obtained phenol compound is reacted in a range of 0.001 to 1.0 mole.

HO-Y-OH (3) (In the formula, Y is selected from the group consisting of a phenylene group, a naphthyl group, or a group represented by the general formula (2) which may have a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent. At least one basis.)

Z-CH ₂ -X-CH ₂ -Z (4) (In the formula, X is selected from the group consisting of phenylene, naphthyl or general formula (2) which may be substituted by a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms. At least one of the groups represented by). Z represents a halogen atom.)

(In the formula, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, which may be the same or different from each other. R ₂ is a single bond or a divalent group.)

The epoxy resin (A) is preferably a phosphorus-containing epoxy resin in a range of 50 to 100% by mass, and the phosphorus-containing epoxy resin has a phosphorus content of 0.5 to 6.0% by mass.

The active hydrogen group of the epoxy resin hardener containing the phenol compound (B) is preferably in the range of 0.4 to 1.2 moles relative to 1 mole of the epoxy group of the epoxy resin (A).

The present invention is a prepreg obtained from the epoxy resin composition described above, an adhesive sheet, an epoxy laminate, an epoxy sealing material, and an epoxy casting material. The present invention is a cured product obtained by curing the aforementioned epoxy resin composition.

The epoxy resin composition of the present invention can provide a hardened product with low dielectric properties and high heat resistance, and is suitable for use in lamination, molding, casting, and bonding.

The epoxy resin composition of this invention contains an epoxy resin (A) and the phenol compound represented by General formula (1) as an essential component.

In the phenol compound (B) represented by the general formula (1), m is the number of repeating units, and the average value must be 0 <m <10, preferably 0.01 <m <8, and more preferably 0.05 <m <5. m = 0, that is, if a phenol compound represented by the general formula (1) is not included, low dielectric properties are not effective, and if m is too large, it may become high viscosity. If m is an average value in a range of 0 <m <10, the effect of low dielectric properties will not be exhibited without a high viscosity. The phenolic hydroxyl equivalent is not particularly limited, but is preferably 1,000 g / eq or less, and more preferably 500 g / eq or less. When the phenolic hydroxyl equivalent is large, the molecular weight becomes large, so that it has a high viscosity, and the heat resistance of the cured product may decrease. Here, the average coefficient is averaged.

X and Y in the general formula (1) are at least one selected from the group consisting of a phenylene group, a naphthyl group, or a group represented by the general formula (2), which may have a substituent, and may be the same or have a phase boundary. When having a substituent, a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom is used as a substituent. Specific examples of such a hydrocarbon group and a halogen atom may be the same as those of R ₁ in the general formula (2) described later.

In the general formula (2), R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, and may be the same or different from each other. Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, A linear or branched alkyl group having 1 to 10 carbon atoms such as n-hexyl, or a cyclic alkyl group having 4 to 10 carbon atoms such as cyclohexyl, or may have phenyl, naphthyl, tolyl, xylyl, Aryl groups having 6 to 10 carbon substituents such as dihydroindenyl, or may have benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2 Substituents such as aralkyl having 7 to 10 carbon substituents such as 6,6-dimethylbenzyl, 3,5-dimethylbenzyl, α-methylbenzyl, etc., and the preferred substituent is methyl. , Ethyl, third butyl, cyclohexyl, phenyl, α-methylbenzyl.

R ₂ is a single bond or a divalent group, and may contain a halogen atom, a hetero element such as a sulfur element, a nitrogen element, and an oxygen element. Specific examples of the divalent base are -CH _2- , -C (CH ₃ ) _2- , -CH (CH ₃ )-, -C (CF ₃ ) _2- , -CO-, -O-, -S -, -SO _2- , benzylidene, α-methylbenzylidene, cyclohexylene, cyclopentylene, 9H-fluorene-9-ylidene, or cyclohexenyl, etc., these groups are aromatic The skeleton may further have a substituent having the same meaning as R ₁ . Preferred divalent radicals are -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -S-, -SO _2- , 9H-fluorene-9-subunit.

In addition, in the general formulae (1) to (4), the same symbols have the same meaning unless otherwise specified.

The phenol compound (B) is obtained by reacting the dihydroxy compound (a) and the halogenated methyl group-containing compound (b).

Conventionally, it has been known to synthesize a polyether by reacting a hydroxyl group as an alkali metal salt with a halide, and to obtain a dihydroxy compound (a) of a phenol compound (B) and a halogenated methyl compound (b ) Reaction, this polyether synthesis method can be used. In addition, m in the general formula (1) can be roughly calculated from the molar ratio of the dihydroxy compound (a) and the halogenated methyl group-containing compound (b). The closer the mole ratio is to 1, the larger m is. However, since it is necessary to have dihydroxy groups at both ends, the ratio of (a) / (b) is greater than 1.

In order to further impart heat resistance, a small amount of trifunctional or higher hydroxy compounds may be used in combination. However, since the cured product is highly elastic, it is allowed to a degree that does not affect the adhesive force.

Specific examples of the dihydroxy compound (a) include dihydroxy compounds containing phenylene such as hydroquinone, resorcinol, and catechol, 1,4-dihydroxynaphthalene, and 1,6-dihydroquinone. Naphthalene diphenols such as hydroxynaphthalene, 2,6-dihydroxynaphthalene, bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, 4,4'-oxygen Divalent phenols such as bisphenol, 4,4'-carbonylbisphenol, bisphenol hydrazone, 4,4'-biphenol, 2,2'-biphenol, bisphenol acetophenone, etc. Compounds such as a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom which are synonymous with R _{1 of the} above-mentioned general formula (2), etc., as a substituent. Preferred examples include 4-hexylresorcinol, 1,6-dihydroxynaphthalene, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol, 4,4'-oxybisphenol, 4,4'-carbonylbisphenol, bisphenol hydrazone, and tetrabromobisphenol A. More preferable examples include tetramethylbisphenol S, bisphenol hydrazone, and tetrabromobis. Phenol A.

Specific examples of the halogenated methyl group-containing compound (b) include dichloromethylbenzene, dichloromethylnaphthalene, dichloromethylbiphenyl, dichloromethylfluorene, and the like. Compounds such as a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom which are synonymous with R _{1 in the} above-mentioned general formula (2), and the like.

The phenol compound (B) is obtained by reacting a dihydroxy compound (a) with a halogenated methyl group-containing compound (b). At this time, it is necessary to react the halogenated methyl-containing compound (b) in a range of 0.001 to 1.0 mol relative to 1.0 mol of the dihydroxy compound (a), preferably in a range of 0.01 to 0.9 mol, more preferably Is in the range of 0.05 to 0.8 moles, and even more preferably in the range of 0.1 to 0.7 moles. The halogenated methyl group-containing compound (b) is 1 mol or more, and the end group of the reaction product becomes a halogen. Therefore, the phenol compound (B) represented by the general formula (1) cannot be obtained.

The reaction system of the dihydroxy compound (a) and the halogenated methyl group-containing compound (b) can be reacted with alkali metal hydrogen such as potassium carbonate, sodium hydroxide, and potassium hydroxide. The reaction is performed in the presence of an oxide, the reaction temperature is 20 to 100 ° C, preferably 50 to 60 ° C, the reaction time is 1 to 10 hours, the reaction does not proceed below 20 ° C, and an electrophilic substitution reaction occurs above 100 ° C. Yu.

The epoxy resin (A) used in the epoxy resin composition of the present invention is not particularly limited as long as it is a well-known epoxy resin, but it is preferably one having an average of 2 to 6 epoxy groups in the molecule. A medium having 2.5 to 5 epoxy groups is more preferred, and a molecule having 3 to 4 epoxy groups is most preferred. Particularly preferred is a Novolak resin. When there are few epoxy groups, there exists a possibility of having a bad influence on the heat resistance of hardened | cured material. When there are many epoxy groups, there exists a possibility that it may have an adverse influence on adhesiveness.

Moreover, when halogen-free and flame retardance are necessary, it is preferable to contain 50 to 100 mass% of a phosphorus-containing epoxy resin, and this phosphorus-containing epoxy resin has a phosphorus content of 0.5 to 6.0 mass%. When the phosphorus content is decreased, even if a flame retardant bone is introduced into the phenol compound (B) of the present invention, or if a filler or a flame retardant auxiliary is used, sufficient difficulty may not be exhibited. When the phosphorus content is large, the flame retardancy can be fully exhibited, but the resin composition may have a high viscosity, or the solvent solubility or water resistance may be deteriorated. In addition, when DOPO is used as the phosphorus supply material, the softening point of the epoxy resin (A) also becomes very high, and the workability of melting, impregnation, and casting is reduced, and the molecular weight of the epoxy resin (A) itself is increased, and the phenol compound is increased. (B) The reactivity is also lowered, so there is a possibility that the effects of heat resistance, adhesiveness, and dielectric properties as a cured product cannot be exhibited. Therefore, it is preferable to control the phosphorus content rate in a range of 0.5 to 6.0% by mass, more preferably 1.0 to 5.0% by mass, and even more preferably 2.0 to 4.0% by mass.

Specific examples of the epoxy resin (A) include Epotohto YD-128, Epotohto YD-8125, Epotohto YD-825GS (Nippon Steel & Sumitomo Chemical Co., Ltd.), bisphenol A-type epoxy resin, Epotohto YDF-170, Epotohto YDF-170B, Epotohto YDF-8170, YDF-870GS (Binphenol F-type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), YSLV-80XY (Tetramethylbisphenol manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) F-type epoxy resin), Epotohto YDC-1312 (hydroquinone epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), jER YX4000H (biphenyl epoxy resin manufactured by Mitsubishi Chemical Corporation), Epotohto YDPN -638, Epotohto YDPN-63X (Nippon Steel & Sumikin Chemical Co., Ltd. phenol Novolak resin), Epotohto YDCN-701 (Nippon Steel & Sumikin Chemical Co., Ltd. cresol Novolak epoxy resin), Epotohto ZX-1201 (Nippon Steel & Sumitomo Chemical Co., Ltd. bisphenol fluorene type epoxy resin), TX-0710 (Nippon Steel & Sumitomo Chemical Co., Ltd. bisphenol S type epoxy resin), Epiclon EXA-1515 (Danippon Chemical Industry Co., Ltd. Bisphenol S type epoxy resin manufactured by Co., Ltd.), NC-3000 (Biphenylaralkylphenol-type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), Epotohto ZX-1355, Epotohto ZX-1711 (naphthalene diphenol-type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epotohto ESN -155 (β-naphthol aralkyl type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epotohto ESN-355, Epotohto ESN-375 (Dinaphthol aralkyl manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Type epoxy resin), Epotohto ESN-475V, Epotohto ESN-485 (α-naphthol aralkyl type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPPN-501H (Shenzhen Chemical Pharmaceutical Co., Ltd. Phenyl Methane-type epoxy resin), Sumiepoxy TMH-574 (ginsylphenyl methane-type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.), YSLV-120TE (bisthioether-type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epotohto ZX-1684 (Resorcinol-type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epiclon HP-7200H (dicyclopentadiene-type epoxy resin manufactured by DIC Corporation), TX-0929, TX -0934, TX-1032 (alkylene glycol epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Celoxide 2021 (aliphatic cyclic epoxy resin manufactured by DAICEL Chemical Industry Co., Ltd.), Epotohto YH-434 ( Diaminodiphenylmethane tetraglycidylamine manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), jER 630 (aminophenol type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd.), Epotohto EX-289B, Epotohto FX-305 TX-0932A (phosphorus-containing epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), urethane modified epoxy resin, oxazolidone ring-containing epoxy resin, etc., but it is not limited to this Wait. These epoxy resins may be used alone or in combination of two or more kinds.

The epoxy resin composition of the present invention must use the phenol compound (B) represented by the aforementioned general formula (1) as a hardener component, but other epoxy resins may be used in combination as long as the object of the present invention is not impaired. Resin hardener.

Specific examples of other epoxy resin hardeners that can be used in combination include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol S, bisphenol Z, bisphenol hydrazone, Tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis (3-methyl-6 -Third-butylphenol), 4,4'-biphenol, 3,3'-5,5'-tetramethyl-4,4'-dihydroxybiphenyl, catechol, resorcinol Phenol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tertiary-butylhydroquinone , Di-tertiary-butyl hydroquinone, dihydroxynaphthalene, dimethylol naphthalene and other divalent phenols, trihydroxynaphthalene, p- (4-hydroxyphenyl) methane, 1,1,2 2,2- (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac, trivalent or higher phenols, co-condensation phenols derived from dicyclopentadiene and phenols, Co-condensation phenols obtained from cresols, formaldehyde and alkoxy substituted naphthalenes, phenol aralkyl-based phenols obtained from phenols and p-Xylenedichloride, etc. , Biphenylaralkyl based phenols obtained from phenols and bischloromethylbiphenyl, naphthol aralkyl based phenols synthesized from naphthols and p-xylene dichloride, etc. . Other epoxy resin hardeners include, for example: methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyroyrellitic anhydride, phthalic anhydride, trimellitic anhydride, methyl Acid anhydrides such as Methylnadic Anhydride, diethylenetriamine, triethylenetetramine, m-xylylenediamine, Isophoronediamine, diaminediphenylmethane, diaminediphenylphosphonium ( Diaminodiphenyl sulfone), diamine diphenyl ether, dicyandiamine, dimer acid and other polycondensates (polyamideamine) and other amine compounds, triphenylphosphine, etc. Isophosphine compounds, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4methylimidazole, 2-undecylimidazole, 1-cyanoethyl -2-methylimidazole and other imidazoles and their salts with trimellitic acid, isotricyanic acid, boron and the like, imidazole salts, benzyldimethylamine, 2,4,6-ginseng (di Amines such as methylaminomethyl) phenol, grade 4 ammonium salts such as trimethylammonium chloride, diazabis Ring compounds and their salts, phenols, phenol novolac resins, and other salts are boron trifluoride, amines, ether compounds, and other compounds, aromatic sulfonium or iodine salts, and the like.

These epoxy resins can be used alone or in combination of two or more kinds. These blending amounts are only required to be within a range that does not impair the object of the present invention, but compared with the total amount of the phenol compound (B) represented by the general formula (1) and other epoxy resin hardeners, It is preferably less than 50% by mass, more preferably less than 40% by mass, and even more preferably less than 25% by mass.

Moreover, in the epoxy resin composition of this invention, the compounding quantity of an epoxy resin hardening | curing agent is an epoxy resin hardening | curing agent containing a phenol compound (B) with respect to 1 mol of epoxy groups of an epoxy resin (A). The active hydrogen group is preferably in the range of 0.4 to 1.2 moles, more preferably 0.5 to 1.1 moles, and still more preferably 0.7 to 1.0 moles. Too little or too much epoxy resin curing agent may cause incomplete hardening compared to epoxy groups, and there is a possibility that good hardened physical properties cannot be obtained. The active hydrogen group of the epoxy resin hardener represents a functional group that reacts with an epoxy group, and specific examples thereof include a phenolic hydroxyl group, an amino group, and a carboxyl group.

A hardening accelerator can be used in the epoxy resin composition of this invention as needed. Specific examples of hardening accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2- (dimethylaminomethyl). ) Tertiary amines such as phenol, 1,8-diaza-bicyclo (5,4,0) undec-7-ene, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine Phosphines such as triphenylborane, and metal compounds such as tin octoate. The hardening accelerator can be used alone or in combination of two or more. Relative to the hair 100 parts by mass of the epoxy resin (A) in the clear epoxy resin composition, and if necessary, 0.02 to 5.0 parts by mass are used. By selectively using these hardening accelerators, the hardening temperature can be reduced and the hardening time can be shortened.

In the epoxy resin composition of the present invention, an organic solvent can also be used for viscosity adjustment. The organic solvent that can be used is not particularly limited, but if it is specifically exemplified, N, N-dimethylformamidine can be exemplified. Amines such as amines, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, and aromatic hydrocarbons such as benzene and toluene. These solvents can be used alone or in combination of two or more kinds.

The epoxy resin composition of this invention can mix | blend a hardening resin or a thermoplastic resin other than an epoxy resin within the range which does not impair the characteristic. Specific examples include phenol resin, acrylic resin, petroleum resin, indene resin, indene-coumarone resins, phenoxy resin, cyanate resin, and epoxy acrylate Resin, vinyl compound, polyurethane, polyester, polyamide, polyimide, polyimide, polyetherimide, bismaleimide-triazine resin ), Polyether hydrazone, polyfluorene, polyether ether ketone, polyphenylene sulfide, and polyvinyl formal (Polyvinyl formal), but it is not limited thereto.

A filler may be used in the epoxy resin composition of the present invention as necessary. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, fired talc, clay, kaolinite, titanium hydroxide, glass powder, and silica dioxide hollow particles (silica balloon). Organic or inorganic moisture-resistant pigments, scaly pigments, and the like. Use general inorganic fillers The reason is, for example, improvement in impact resistance. Fibrous fillers such as glass fibers, pulp fibers, synthetic fibers, and ceramic fibers, or organic fillers such as particulate rubber and thermoplastic elastomers can be blended.

In addition, additives such as a flame retardant, a shake modifier, and a fluidity promoter may be blended in the epoxy resin composition of the present invention as necessary. Examples of the shake-modifying and modifying material include silicone, castor oil, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite. Further, if necessary, a release agent such as coconut wax (Carnauba-wax), OP wax, a coloring agent such as carbon black, a flame retardant such as antimony trioxide, and low stress such as silicone oil can be blended in the resin composition of the present invention Chemical agents, lubricants such as calcium stearate.

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

Next, the adhesive sheet obtained using the epoxy resin composition of this invention is demonstrated. The method for manufacturing the adhesive sheet is not particularly limited, but it is insoluble in epoxy resin such as polyester film and polyimide film. The carrier film of the composition is preferably coated with the epoxy resin composition of the present invention to a thickness of 5 to 100 μm, and then heated and dried at 100 to 200 ° C. for 1 to 40 minutes to form a sheet. A method generally called a casting method to form a resin sheet. If the epoxy resin composition-coated sheet is surface-treated with a release agent beforehand, the formed adhesive sheet can be easily peeled off. Here, the thickness of the adhesive sheet is desirably formed to 5 to 80 μm. The adhesive sheet obtained by such a method is generally an insulating adhesive sheet having insulation, but a conductive adhesive sheet can be obtained by mixing a conductive metal or metal-coated fine particles in an epoxy resin composition.

In addition, a method for manufacturing a laminated board using the prepreg or the insulating adhesive sheet of the present invention will be described. When a prepreg is used to form a laminated board, one or more prepregs are laminated, and metal foils are arranged on one or both sides to form a laminate. This laminate is laminated and integrated by heating and pressing. Here, as the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel can be used. The heating and pressurizing conditions of the laminate may be appropriately adjusted by heating and pressing the conditions under which the epoxy resin composition is hardened. However, if the pressing pressure is too low, air bubbles may remain inside the obtained laminate. The electrical characteristics are reduced, so it is appropriate to pressurize to meet the conditions of moldability. For example, the temperature can be set to 160 to 220 ° C, the pressure can be set to 49.0 to 490.3 N / cm ² (5 to 50 kgf / cm ² ), and the heating time can be set to 40 to 240 minutes. Furthermore, a single-layer laminated board obtained by such a method can be used as an inner layer material to produce a multilayer board. At this time, a circuit is first formed on the laminated board by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution and blackened to obtain an inner layer material. In this inner layer, one side or both sides of the circuit forming surface are formed with a prepreg or an insulating adhesive sheet to form an insulating layer, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board. When an insulating adhesive layer is used to form an insulating layer, an insulating adhesive sheet is arranged on the circuit formation surface of a plurality of inner layers to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminated material is integrally molded by heating and pressing to form a hardened material of an insulating adhesive sheet as an insulating layer, and at the same time, a multilayered inner layer material is formed. A metal foil in which an inner layer material and a conductor layer are formed by using a cured material of an insulating adhesive sheet as an insulating layer. Here, the metal foil can be the same as the user of the laminated board used for the inner layer material. The heating and pressure forming system can be performed under the same conditions as the forming of the inner layer material. When the laminated board is coated with an epoxy resin composition to form an insulating layer, the outermost circuit forming surface resin of the inner layer material is coated with the aforementioned epoxy resin composition at a thickness of preferably 5 to 100 μm, and then 100 to 200. Heat to dry at 1 ° C for 90 minutes to form flakes. Generally formed by a method called a casting method. The thickness after drying is preferably 5 to 80 μm. On the surface of the multi-layer laminated board formed by such a method, a via hole or a circuit can be formed by an addition method or a subtractive method to form a printed wiring board. Furthermore, by using the printed wiring board as an inner layer material and repeating the aforementioned method, a multi-layer laminated board can be formed. In the case of forming an insulating layer with a prepreg, one or a plurality of laminated prepregs are arranged on the circuit formation surface of the inner layer material, and a metal foil is further arranged on the outer side to form a laminate. Then, the laminate is integrally formed by heating and pressing to form a hardened body of the prepreg as an insulating layer, and at the same time, an outer metal foil is used as a conductor layer. Here, the metal foil may be the same as a user of a laminated board used as an inner layer board. The heating and pressure forming system can be performed under the same conditions as the forming of the inner layer material. On the surface of the multi-layer laminated board formed by such a method, a via hole or a circuit can be formed by an addition method or a subtractive method to form a printed wiring board. Furthermore, by using the printed wiring board as an inner layer material and repeating the aforementioned method, a multilayer laminated board can be further formed.

In addition, when the epoxy resin composition of the present invention is cured by heating, an epoxy resin cured product can be formed. This cured product is excellent in terms of low dielectric properties, heat resistance, and low hygroscopicity. This hardened material can be obtained by molding and processing the epoxy resin composition by methods such as casting, compression forming, and transfer forming. 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, encapsulant, casting, and hardened material obtained by using the composition have excellent low dielectric properties, heat resistance, and low hygroscopicity. 2. Those who show excellent characteristics in adhesiveness.

(Example)

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited thereto. In the examples, unless otherwise stated, parts represent "mass parts" and% represents "mass%".

(1) Determination of epoxy equivalent

Measured in accordance with JIS K7236. Specifically, a potentiometric titration device was used, methyl ethyl ketone was used as a solvent, a tetraethylammonium bromide acetic acid solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was used.

(2) Measurement of phosphorus content

Add sulfuric acid, hydrochloric acid, perchloric acid to the sample, heat and wet ash, All phosphorous atoms are regarded as orthophosphoric acid. The metavanadate and molybdate are reacted in an acidic solution of sulfuric acid, and the absorbance of the phosphorous vanadium molybdate (Phospho vanado molybdate) acid complex is measured at 420 nm. The phosphorus atom content is expressed in%. A B-stage resin powder was used as a sample for measuring the epoxy resin composition.

(3) Determination of phenolic hydroxyl equivalent

Add THF containing 4% methanol and 10% tetrabutylammonium hydroxide to the sample, and measure the absorbance between 400nm and 250nm with an ultraviolet-visible spectrophotometer, and find the phenolic hydroxyl group as the equivalent of each hydroxyl group. The number of g of sample.

(4) Measurement of water absorption

According to JIS C 6481, the measurement was performed based on the weight change before and after immersion in water at 23 ° C for 24 hours.

(5) Determination of specific permittivity and dissipation factor

The value of 1 GHz was measured by a cavity resonance method (Vector network analyzer (VNA) E8363B (manufactured by Agilent Technologies) and a resonance cavity disturbance method dielectric rate measurement device (manufactured by Kanto Electronics Application Development)).

(6) Measurement of adhesive force

According to JIS K 6854-1 by Shimadzu Corporation, an Autograph was measured at a temperature of 25 ° C. at 50 mm / min.

(7) Measurement of water resistance

The heat resistance of the solder after PCT was measured as an index of water resistance. A test piece prepared in accordance with JIS C 6481 was treated in an autoclave at 121 ° C and 0.2MPa for 3 hours, and then immersed in a solder bath at 260 ° C. 20 More than minutes Those who did not swell or fall off were rated ○, those who did not swell or swelled within 10 were rated ╳, and others were rated △.

(8) T-288 test

The measurement was performed by the method according to IPC TM-650.

(9) Measurement of glass transition temperature

Measured in accordance with JIS K 7121 differential scanning calorimetry. The EXTER DSC6200 manufactured by SII was used to measure from 20 ° C at a temperature increase rate of 10 ° C / min, and the extrapolated glass transition start temperature (Tig) of the DSC chart obtained in the second cycle was obtained.

(10) Measurement of flame resistance

The copper foil was removed from the copper laminate by immersion in an etchant. After washing and drying, a test piece with a length of 127 mm and a width of 12.7 mm was cut and tested in accordance with UL94 (Underwriters Laboratories Inc.'s safety certification standard). Method (V method) to ignite to measure the burning time. Evaluations are recorded as V-0, V-1, V-2. However, the complete burner is recorded as "burning".

Synthesis example 1 (synthesis of phenol compound (B1))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling pipe, and a nitrogen introduction device, 806 parts of methanol and 201.7 parts of potassium hydroxide were added, and the mixture was stirred. Then, bis ( 550 parts of 4-hydroxy-3,5-dimethylphenyl) fluorene (hereinafter, TMBPS) to form an alkali metal salt. Thereafter, 4.5 parts of 4,4'-bischloromethylbiphenyl (hereinafter, BCMB) as a halogenated methyl-containing compound (b) and 488 parts of bis (2-methoxyethyl) ether as a solvent were added. The temperature was raised to 75 ° C while stirring, and the reaction was performed for 2 hours.

After the reaction is completed, the generated salt is removed by filtration. The temperature was raised to 100 ° C. under reduced pressure, and methanol and bis (2-methoxyethyl) ether were distilled off. Then, 1,290 parts of toluene was added and dissolved. After neutralizing and separating with phosphoric acid, the solution was further washed and separated twice with water, and then toluene was distilled off to obtain 526 parts of a phenol compound (B1) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 156 g / eq.

Synthesis example 2 (synthesis of phenol compound (B2))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, 367 parts of methanol and 91.7 parts of potassium hydroxide were added and stirred, and 250 parts of TMBPS as the dihydroxy compound (a) was added. To form an alkali metal salt. Thereafter, 61.5 parts of BCMB as the halogenated methyl group-containing compound (b) and 360 parts of bis (2-methoxyethyl) ether as a solvent were added, and the temperature was raised to 75 ° C. with stirring while reacting for 2 hours.

After the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg. After the entire amount of methanol and bis (2-methoxyethyl) ether was distilled off, 685 parts of toluene was added to dissolve. After neutralizing and separating the solution with phosphoric acid, the solution was further washed and separated twice with water, and then toluene was distilled off to obtain 279 parts of a phenol compound (B2) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 250 g / eq.

Synthesis example 3 (synthesis of phenol compound (B3))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, 323 parts of methanol and 80.7 parts of potassium hydroxide were added, stirred, and then TMBPS 220 as the dihydroxy compound (a) was added. Parts to form an alkali metal salt. Thereafter, 690.2 parts of BCMB as a halogenated methyl group-containing compound (b) and bis (2-methoxyethyl) ether 401 as a solvent were added. The temperature was raised to 75 ° C while stirring, and the reaction was carried out for 2 hours.

After the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg. After methanol and bis (2-methoxyethyl) ether were distilled off, 663 parts of toluene was added to dissolve. After neutralizing and separating with phosphoric acid, the solution was further washed and separated twice with water, and toluene was distilled off to obtain 261 parts of a phenol compound (B3) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 432 g / eq.

Synthesis example 4 (synthesis of phenol compound (B4))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, 293 parts of methanol and 73.3 parts of potassium hydroxide were added, stirred, and TMBPS 200 as the dihydroxy compound (a) was added. Parts to form an alkali metal salt. Thereafter, 114.8 parts of BCMB as the halogenated methyl group-containing compound (b) and 441 parts of bis (2-methoxyethyl) ether as a solvent were added, and the temperature was raised to 75 ° C. with stirring while reacting for 2 hours.

After the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg. After methanol and bis (2-methoxyethyl) ether were distilled off, 657 parts of toluene was added to dissolve. After neutralizing and separating with phosphoric acid, the solution was further washed and separated twice with water, and then toluene was distilled off to obtain 253 parts of a phenol compound (B4) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 702 g / eq.

Synthesis example 5 (synthesis of phenol compound (B5))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, 293 parts of methanol and 73.3 parts of potassium hydroxide were added, stirred, and TMBPS 200 as the dihydroxy compound (a) was added. Parts to form an alkali metal salt. Thereafter, 123 parts of BCMB as the halogenated methyl group-containing compound (b) and 460 parts of bis (2-methoxyethyl) ether as a solvent were added, and the temperature was raised to 75 ° C. with stirring while reacting for 2 hours.

After completion of the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg. After all the methanol and bis (2-methoxyethyl) ether were distilled off, 670 parts of toluene was added and dissolved. After neutralizing and separating the solution with phosphoric acid, the solution was further washed and separated twice with water, and then toluene was distilled off to obtain 230 parts of a phenol compound (B5) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 1018 g / eq.

Synthesis example 6 (synthesis of phenol compound (B6))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, 293 parts of methanol and 73.3 parts of potassium hydroxide were added, and 200 parts of TMBPS as the dihydroxy compound (a) was added. Alkali metal salts are formed. Then, 57.2 parts of dichloromethylbenzene (P-xylyl dichloride; PXDC) as a halogenated methyl group-containing compound (b) and 307 parts of bis (2-methoxyethyl) ether as a solvent were added, The temperature was raised to 75 ° C while stirring, and the reaction was performed for 2 hours.

After the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg. After methanol and bis (2-methoxyethyl) ether were distilled off, 544 parts of toluene was added to dissolve. After neutralizing and separating the solution with phosphoric acid, the solution was further washed and separated twice with water, and then toluene was distilled off to obtain 215 parts of a phenol compound (B6) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 399 g / eq.

Synthesis example 7 (synthesis of phenol compound (B7))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, 438 parts of methanol and 109.6 parts of potassium hydroxide were added, and then tetramethylbis as a dihydroxy compound (a) was added. 250 parts of phenol F (hereinafter, TMBPF) forms an alkali metal salt. Thereafter, 51.2 parts of PXDC as a halogenated methyl group-containing compound (b) and 265 parts of bis (2-methoxyethyl) ether as a solvent were added, and the temperature was raised to 75 ° C. with stirring while reacting for 2 hours.

After completion of the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg. After all the methanol and bis (2-methoxyethyl) ether were distilled off, 653 parts of toluene was added to dissolve. After neutralizing and separating the solution with phosphoric acid, the solution was further washed and separated twice with water, and then toluene was distilled off to obtain 266 parts of a phenol compound (B7) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 213 g / eq.

Synthesis example 8 (synthesis of phenol compound (B8))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device, 257 parts of methanol and 64.1 parts of potassium hydroxide were added, and then bisphenol hydrazone (a) was added as a dihydroxy compound (a). Hereinafter, 200 parts of BPFL) are formed to form an alkali metal salt. Thereafter, 71.7 parts of BCMB as the halogenated methyl group-containing compound (b) and 378 parts of bis (2-methoxyethyl) ether as a solvent were added, and the temperature was raised to 75 ° C. with stirring while reacting for 2 hours.

After the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C. under a reduced pressure of 50 mmHg. After methanol and bis (2-methoxyethyl) ether were distilled off, 585 parts of toluene was added to dissolve. After neutralizing and separating with phosphoric acid, the solution was further washed and separated twice with water, and toluene was distilled off to obtain a pale yellow solid phenolation. Compound (B8): 203 parts. The phenolic hydroxyl equivalent of the obtained phenol compound was 484 g / eq.

Synthesis example 9 (synthesis of phenol compound (B9))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling pipe, and a nitrogen introduction device, 219 parts of methanol and 54.8 parts of potassium hydroxide were added, and 125 parts of TMBPF as a dihydroxy compound (a) was added. To form an alkali metal salt. Then, 55 parts of 1,5-bischloromethylnaphthalene (hereinafter BCMN) as the halogenated methyl group-containing compound (b) and 201 parts of bis (2-methoxyethyl) ether as a solvent were added, while stirring. The temperature was raised to 75 ° C, and the reaction was carried out for 2 hours.

After completion of the reaction, the produced salt was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg. After all the methanol and bis (2-methoxyethyl) ether were distilled off, 393 parts of toluene was added to dissolve. After neutralizing and separating the solution with phosphoric acid, the solution was further washed and separated twice with water, and then toluene was distilled off to obtain 142 parts of a phenol compound (B9) as a pale yellow solid. The phenolic hydroxyl equivalent of the obtained phenol compound was 370 g / eq.

Synthesis example 10 (synthesis of epoxy resin (A3))

YDPN-638 (Nippon Steel & Sumikin Chemical Co., Ltd., Novolak) epoxy resin, in a 4-necked glass separable flask equipped with a stirring device, thermometer, cooling tube, and nitrogen introduction device, Epoxy equivalent = 177g / eq) 359 parts were reacted with 141 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA: Sanguang Co., Ltd.) at 160 ° C for 4 hours, A phosphorus-containing epoxy resin (A2) was obtained. The epoxy equivalent of the obtained epoxy resin was 370 g / eq, and phosphorus content rate was 4.0%.

Synthesis example 11 (synthesis of epoxy resin (A6))

In a 4-necked glass separable flask equipped with a stirring device, a thermometer, a cooling pipe, and a nitrogen introduction device, 67 parts of HCA, 48 parts of 1,4-naphthoquinone, and 142 parts of toluene were stirred at 75 ° C for 30 minutes, and then After dehydration reaction at 110 ° C for 90 minutes, 518 parts of ESN-485 (naphthol aralkyl-type epoxy resin, epoxy equivalent = 296 g / eq, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was added, and then toluene was removed by heating up. Thereafter, 0.01 part of triphenylphosphine (TPP) as a catalyst was added and reacted at 160 ° C for 4 hours to obtain a phosphorus-containing epoxy resin (A5). The equivalent weight of the obtained epoxy resin was 551 g / eq, and the phosphorus content rate was 1.5%.

Synthesis example 12 (synthesis of epoxy resin (A7))

In a 4-necked glass separable flask equipped with a stirring device, thermometer, cooling tube, and nitrogen introduction device, 70 parts of HCA, 25 parts of 1,4-naphthoquinone, and 148 parts of toluene were stirred at 75 ° C. for 30 minutes, and then stirred. After dehydration reaction at 110 ° C for 90 minutes, 540 parts of NC-7700 (produced by Nippon Kayaku Co., Ltd., β-naphthol cresol condensed epoxy resin, epoxy equivalent weight = 222 g / eq) was added, and toluene was removed by heating. Then, 0.01 part of TPP as a catalyst was added, and it reacted at 160 degreeC for 4 hours, and obtained the phosphorus-containing epoxy resin (A6). The equivalent weight of the obtained epoxy resin was 372 g / eq, and the phosphorus content rate was 1.5%.

The epoxy resin, hardener, and hardening accelerator used by the Example and the comparative example are as follows.

Epoxy resin (A)

(A1): YDPN-638 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Novolak epoxy resin, epoxy equivalent = 177g / eq)

(A2): ESN-485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., naphthol aralkyl epoxy resin, epoxy equivalent = 296eq)

(A3): Epoxy resin of Synthesis Example 10

(A4): TX-0821 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., phosphorus-containing epoxy resin, epoxy equivalent = 536g / eq, phosphorus content rate = 3.0%)

(A5): TX-1106B (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., phosphorus-containing epoxy resin, epoxy equivalent = 385g / eq, phosphorus content rate = 2.5%)

(A6): Epoxy resin of Synthesis Example 11

(A7): Epoxy resin of Synthesis Example 11

Hardener (B)

(B1): Phenol compound of Synthesis Example 1

(B2): Phenol compound of Synthesis Example 2

(B3): phenol compound of Synthesis Example 3

(B4): Phenol compound of Synthesis Example 4

(B5): Phenol compound of Synthesis Example 5

(B6): Phenol compound of Synthesis Example 6

(B7): Phenol compound of Synthesis Example 7

(B8): Phenol compound of Synthesis Example 8

(B9): Phenol compound of Synthesis Example 9

(B10): ShonolBRG-557 (manufactured by Showa Denko Corporation, Novolak resin, phenolic hydroxyl equivalent = 105g / eq, softening point = 86 ° C)

(B11): TH-2500 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., bisphenol A type phenol resin, phenolic hydroxyl equivalent = 240g / eq, softening point = 82 ° C)

(B12): dicyandiamide (DICY, active hydrogen equivalent = 21g / eq)

Hardening accelerator

(C1): Curazole2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd., 2-ethyl-4-methylimidazole)

Examples 1 to 12 and Comparative Examples 1 to 2

The formulation shown in Table 1 was homogenized while heating the hardener (B) to 120 ° C in the hydroxy-heated epoxy resin (A) to obtain an epoxy resin composition. After the obtained epoxy resin composition was degassed under reduced pressure at the same temperature, a hardening accelerator was added to carefully homogenize it to prevent air bubbles from being cast into the mold, and then cured in a hot air circulation oven at 150 ° C for 2 hours. Then, it hardened at 180 degreeC for 3 hours, and obtained the hardened | cured material. The evaluation results of the obtained cast hardened materials are shown in Table 1.

Examples 13 to 18 and Comparative Examples 3 to 8

According to the formula shown in Table 2, mix epoxy resin (A), hardener (B), Hardening accelerator and solvent to obtain epoxy resin composition varnish with 50% non-volatile content. The epoxy resin (A), the hardener (B), and the hardening accelerator are used by dissolving in methyl ethyl ketone (MEK) in advance. A glass cloth (manufactured by Nittobo Co., Ltd., IPC specification 2116) was impregnated with the obtained epoxy resin composition varnish, and the impregnated cloth was dried in a hot air circulation oven at 150 ° C. for 7 minutes to obtain a B-stage preform. Dipping. One of the obtained prepregs was used for layer formation, and 4 pieces of prepregs were overlapped with copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, 35 μm thick) at 130 ° C for 15 minutes + 190 ° C. A vacuum pressing of 2 MPa was performed at a temperature condition of X80 minutes to obtain a 0.5 mm thick laminated board. The other is for the measurement of dielectric properties. The purpose is to mold the resin alone. Use about 10g of B-stage resin powder obtained by pulverizing several prepregs. Use a Teflon frame mold to press the same vacuum. The hardening conditions resulted in a 2 mm thick resin plate. The evaluation results of the obtained molded articles are shown in Table 2.

(Industrial availability)

The epoxy resin composition-based hardened material of the present invention has lower dielectric properties than conventional epoxy resin compositions and has good heat resistance, so it can be used. It is used for electronic circuit boards or encapsulants that require electrical insulation and high reliability, especially for micro-wiring electronic circuit boards.

Claims (7)

An epoxy resin composition comprising an epoxy resin (A) and a phenol compound (B) represented by the general formula (1); wherein 1 mol of epoxy resin relative to the epoxy resin (A) , The active hydrogen group of the epoxy resin hardener containing the aforementioned phenol compound (B) is in the range of 0.4 to 1.2 moles; In the formula, m is the number of repeating units, and the average value is 0 <m <10. X and Y are selected from the group consisting of phenylene, naphthyl or general formula, which may be substituted by a hydrocarbon group or a halogen atom having 1 to 10 carbon atoms. (2) at least one of the bases represented may be the same or different; In the formula, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, which may be the same or different from each other; R ₂ is a single bond or a divalent group. The epoxy resin composition according to item 1 of the scope of patent application, wherein the phenol compound (B) is 1 mole relative to the dihydroxy compound (a) represented by the following general formula (3), so that A phenol compound (B) obtained by reacting a halogenated methyl group-containing compound (b) represented by the general formula (4) in a range of 0.001 or more and less than 1.0 mole; HO-Y-OH (3) In the formula, Y selected from the group consisting of carbon atoms may have a hydrocarbon group or a halogen atom as a substituent group of the phenylene group, a naphthyl group or a stretch of formula (2) is at least one group of 1 to _{10; Z-CH 2 -X-CH} 2 -Z (4) In the formula, X is at least one group selected from the group consisting of a phenylene group, a naphthyl group, or a group represented by the general formula (2), which may have a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent; Z is a halogen atom; In the formula, R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, which may be the same or different from each other; R ₂ is a single bond or a divalent group. The epoxy resin composition according to item 1 of the scope of patent application, wherein the aforementioned epoxy resin (A) is an epoxy resin containing 50 to 100% by mass of phosphorous, and the phosphorous epoxy resin has 0.5 A phosphorus content of 6.0% by mass. A prepreg characterized by using the epoxy resin composition described in any one of claims 1 to 3 of the scope of patent application. An adhesive sheet characterized by using the epoxy resin composition described in any one of claims 1 to 3 of the patent application scope. An epoxy resin laminated board characterized by using the epoxy resin composition described in any one of claims 1 to 3 of the scope of patent application. A hardened product is a hardened product obtained by hardening the epoxy resin composition described in any one of claims 1 to 3.