TW201516070A - Epoxy resin composition and cured product thereof - Google Patents

Abstract

The present invention provides an epoxy resin composition and a cured product thereof, which are excellent in low dielectric property and high thermal endurance, and useful in the purpose of laminating, casting, injecting and adhesion. Provided is a epoxy resin composition and a cured product thereof, which comprises an epoxy resin (A) represent by formula (1), and a curing agent (B). (in the formula, m is a repeat number with an average of 0 < m < 10. n is a repeat number with an average of 0 ≤ n < 10. X, Y are at least one group selected from a phenylene group, a naphthylene group or a group represented by formula (2), which may has a substituent of an alkyl group with a carbon number of 1 to 10 or halogen atom, and which may be the same or different.) (in the formula, R1 represents a hydrogen atom, an alkyl group with a carbon number of 1 to 10 or a halogen atom, which may be the same or different. R2 represents a single bond or a divalent group).

Description

Epoxy resin composition and cured product thereof

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

In recent years, the demand for small mobile communication devices such as smart phones or tablet computers has grown rapidly. Accordingly, the signal bandwidth of the information communication machine and the CPU frequency of the computer reach the GHZ frequency domain, and further high frequency is gradually advanced.

The dielectric loss of an electrical signal is proportional to the product of the square root of the specific dielectric of the insulator forming the loop, 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 can weaken the electrical signal of the information and damage the reliability of the signal. Therefore, in order to suppress the insulator used for this, it is necessary to select a material having a dielectric constant and a dielectric loss tangent (Patent Document 1).

The representative insulating material used in the above communication device may, for example, be an epoxy resin, but for example, even in a printed laminate, of course It is required to impart basic properties such as heat resistance or adhesion which are small in dielectric constant and dielectric loss tangent and are the same as in the related art. Recently, it has continued to implement halogen-free flame retardation in response to the environment.

In the halogen-free flame retardation process, many reports propose the reaction of a reactive phosphorus compound 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) with an epoxy group. The method. In order to improve the flame retardancy, it is necessary to increase the phosphorus content, and the number of epoxy groups contained in one molecule is lowered, and the problem that the crosslinking density of the cured product is lowered and the heat resistance is deteriorated still exists.

For this problem, attempts have been made to use polyfunctional epoxy resins and polyfunctional hardeners to improve the crosslink density, but by this method, the hardened material becomes brittle and reduces the good adhesion of the epoxy resin, not only that. At the same time, as the epoxy resin hardening reaction increases, the concentration of hydroxyl groups formed in the cured product also increases, which causes a significant problem of deterioration in dielectric properties.

That is to say, this fact means that a material which satisfies the characteristics of the heat-reducing property which is contrary to the required heat resistance or flame retardancy and the improvement of the strength of the adhesive force does not exist, and is in the design concept of the conventional epoxy resin and hardener. It is a very difficult subject to solve this problem.

For such a difficult problem, many reports have proposed techniques for improving the use of a cyanate compound in combination with an epoxy resin and a hardener. These materials are effective in improving the dielectric properties. However, as the amount of use increases, the cured product becomes hard, and it is difficult to sufficiently satisfy the adhesiveness, the flame retardancy, and the workability (Patent Document 2).

Another low dielectric material is polyphenylene ether resin and phenol There are also many reports on the combination of modified phenolic compounds and epoxy resins. Here, the modified phenol material to which the low dielectric material is imparted is recombined by decomposition during the synthesis, and the molecular weight is inevitably increased, resulting in a decrease in workability such as glass cloth (Glass Cloth) or the like. The point of expensive raw materials is also very unfavorable for the development of the use of communication terminal devices that are becoming more and more popular (Patent Document 3).

[Previous Technical Literature] [Patent Literature]

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

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

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

Therefore, the object of the present invention is to provide 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 the like.

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

(wherein m is the number of repeating units, and the average value is 0 < m < 10. X, Y is selected from a stretching phenyl group, an anthranyl group or a through group which may have a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent. At least one of the groups represented by the formula (2) may be the same or different.

(wherein 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.)

In addition, the phenol compound (B) is preferably a halogenated methyl compound represented by the following formula (4) with respect to 1 mol of the dihydroxy compound (a) represented by the following formula (3). (b) The obtained phenol compound is reacted in the range of 0.001 to 1.0 mol.

HO-Y-OH (3) (wherein Y is selected from a group consisting of a phenyl group having a carbon number of 1 to 10 or a halogen atom as a substituent, a naphthyl group or a group represented by the formula (2) At least one base.)

Z-CH ₂ -X-CH ₂ -Z (4) (wherein X is selected from a phenyl group, an extended naphthyl group or a formula (2) which may have a hydrocarbon group having a carbon number of 1 to 10 or a halogen atom as a substituent At least one of the groups represented by the formula. Z is a halogen atom.)

(wherein 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.)

Further, it is preferable that the epoxy resin (A) is 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.

Moreover, it is preferable that the active hydrogen group of the epoxy resin hardener containing the phenol compound (B) is in the range of 0.4 to 1.2 mol with respect to the epoxy group 1 mol of the epoxy resin (A).

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

The epoxy resin composition of the present invention can provide a cured product excellent in low dielectric properties and high heat resistance, and is suitably used in applications such as lamination, molding, casting, and the like.

The epoxy resin composition of the present invention contains an epoxy resin (A) and a phenol compound represented by the formula (1) as essential components.

In the phenol compound (B) represented by the formula (1), m is the number of repeating units, and the average value must be 0 < m < 10, preferably 0.01 < m < 8, more preferably 0.05 < m < 5. When m = 0, that is, if the phenol compound represented by the formula (1) is not contained, the low dielectric property is ineffective, and if m is too large, it becomes a high viscosity. If m is in the range of 0 < m < 10, it does not become high viscosity, and the effect of low dielectric properties can be exhibited. Further, the phenolic hydroxyl equivalent is not particularly limited, but is preferably 1000 g/eq or less, more preferably 500 g/eq or less. When the phenolic hydroxyl group is large, the molecular weight becomes large, so that it has a high viscosity and the heat resistance of the cured product is lowered. Here, the average coefficient is averaged.

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

In the formula (2), R ₁ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom 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, t-butyl, t-butyl, n-pentyl, a linear or branched alkyl group having 1 to 10 carbon atoms such as n-hexyl group or a cyclic alkyl group having 4 to 10 carbon atoms such as a cyclohexyl group, or may have a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. An aryl group having a carbon number of 6 to 10, such as a dihydroindenyl group, or an benzyl group, a phenethyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, or 2 a substituent such as an aralkyl group having a substituent of 7 to 10 carbon atoms such as 6-dimethylbenzyl group, 3,5-dimethylbenzyl group or α-methylbenzyl group, and a preferred substituent is a methyl group. , ethyl, tert-butyl, cyclohexyl, phenyl, α-methylbenzyl.

R ₂ is a single bond or a divalent group, and may contain a halogen atom and a hetero element such as a sulfur element, a nitrogen element, or an oxygen element. Specific examples of the divalent group can be exemplified by -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. Further, the skeleton may have a substituent synonymous with R ₁ . Preferred divalent bases are -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, -S-, -SO ₂ -, 9H-芴-9-subunits.

Further, among the general formulae (1) to (4), the same symbols have the same meanings unless otherwise specified.

The phenol compound (B) described above is obtained by first reacting the above-described dihydroxy compound (a) with the above-mentioned halogenated methyl group-containing compound (b).

Conventionally, a polyether is synthesized by reacting a hydroxyl group as an alkali metal salt with a halide, and a dihydroxy compound (a) and a halogenated methyl group-containing compound (b) for obtaining a phenol compound (B) are known. In this reaction, the polyether synthesis method can be used. Further, m of the formula (1) can be roughly calculated from the molar ratio of the dihydroxy compound (a) to the halogenated methyl group-containing compound (b). The closer the molar ratio is to 1, the larger m is. However, since it is necessary to have a dihydroxy group at both ends, the ratio of (a) / (b) is greater than 1.

In addition, when the heat resistance is further imparted, a trifunctional or higher hydroxy compound is used in combination in a small amount, and the effect is exhibited. However, since the cured product is highly elasticized, it is allowed to have no influence on the adhesion force.

Specific examples of the dihydroxy compound (a) include hydroxyl-containing dihydroxy compounds such as hydroquinone, resorcin, and catechol, 1,4-dihydroxynaphthalene, 1,6-di. Naphthalenediols such as hydroxynaphthalene and 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'-carbonyl bisphenol, bisphenol oxime, 4,4'-biphenol, 2,2'-biphenol, bisphenol acetophenone, etc., further may be exemplified A hydrocarbon group having 1 to 10 carbon atoms or a halogen atom as a substituent, which has the same meaning as R _{1 of the} above formula (2), and the like. Preferred examples thereof include 4-hexyl resorcinol, 1,6-dihydroxynaphthalene, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, and tetramethylbisphenol. 4,4'-oxybisphenol, 4,4'-carbonyl bisphenol, bisphenol oxime, tetrabromobisphenol A, more preferably tetramethyl bisphenol S, bisphenol oxime, tetrabromo double Phenol A.

Specific examples of the halogenated methyl group-containing compound (b) include dichloromethylbenzene, dichloromethylnaphthalene, dichloromethylbiphenyl, dichloromethylhydrazine, etc., and further may be exemplified. A hydrocarbon having 1 to 10 carbon atoms or a halogen atom, which is synonymous with R _{1 of the} above 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 group-containing compound (b) in the range of 0.001 to 1.0 mol with respect to 1.0 mol of the dihydroxy compound (a), preferably in the range of 0.01 to 0.9 mol, more preferably The range is from 0.05 to 0.8 mol, and a still more preferred range is from 0.1 to 0.7 mol. The compound (b) containing a halogenated methyl group is 1 mol or more, and the terminal group of the reaction product becomes a halogen, so that the phenol compound (B) represented by the formula (1) cannot be obtained.

The reaction of the dihydroxy compound (a) with the halogenated methyl group-containing compound (b) may be an alkali metal hydrogen such as potassium carbonate, sodium hydroxide or potassium hydroxide. 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 the electrophilic substitution reaction occurs above 100 ° C. Hey.

The epoxy resin (A) used in the epoxy resin composition of the present invention is not particularly limited as long as it is a known epoxy resin, but it is preferably a molecule having an average of 2 to 6 epoxy groups in the molecule. It is more preferred to have an average of 2.5 to 5 epoxy groups in the middle, and an average of 3 to 4 epoxy groups in the molecule is preferred. Particularly preferred is a novolak type resin. If the number of epoxy groups is small, the heat resistance of the cured product is adversely affected. If there are many epoxy groups, there is a bad influence on the adhesion.

Further, when halogen-free and flame retardancy is necessary, it is preferable to contain 50 to 100% by mass of a phosphorus-containing epoxy resin having a phosphorus content of 0.5 to 6.0% by mass. When the phosphorus content is reduced, even if a flame retardant skeleton is introduced into the phenol compound (B) of the present invention, or a filler or a flame retardant aid is used, sufficient urgency cannot be exhibited. When the phosphorus content is large, the flame retardancy is sufficiently exhibited, but the resin composition becomes high in viscosity, or the solvent solubility or water resistance is deteriorated. Further, when DOPO is used as the phosphorus supply raw material, the softening point of the epoxy resin (A) is also extremely high, the workability of melting or impregnation, casting is lowered, and the molecular weight of the epoxy resin (A) itself is increased, and the phenol compound The reactivity of (B) is also lowered, so that the effect of heat resistance, adhesion, and dielectric properties of the cured product cannot be exhibited. Therefore, the phosphorus content is preferably controlled in the range of 0.5 to 6.0% by mass, more preferably in the range of 1.0 to 5.0% by mass, and still more preferably in the range of 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 Sumikin Chemical Co., Ltd. bisphenol A type epoxy resin), Epotohto YDF-170, Epotohto YDF-170B, Epotohto YDF-8170, YDF-870GS (Nippon Steel Sumikin Chemical Co., Ltd. bisphenol F-type epoxy resin), YSLV-80XY (Nippon Steel Sumikin Chemical Co., Ltd. made tetramethyl bisphenol F-type epoxy resin), Epotohto YDC-1312 (hydroquinone epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epotohto YDPN -638, Epotohto YDPN-63X (Nippon Steel Sumikin Chemical Co., Ltd. phenol Novolak type resin), Epotohto YDCN-701 (Nippon Steel Sumikin Chemical Co., Ltd. cresol Novolak type epoxy resin), Epotohto ZX-1201 (Nippon Steel & Sumitomo Chemical Co., Ltd. made bisphenol oxime epoxy resin), TX-0710 (Nippon Steel & Sumitomo Chemical Co., Ltd. bisphenol S type epoxy resin), Epiclon EXA-1515 (Dainipic Chemical Industry) Co., Ltd. Bisphenol S-type epoxy resin), NC-3000 (Biphenyl aralkyl phenol epoxy resin manufactured by Nippon Kayaku Co., Ltd.), Epotohto ZX-1355, Epotohto ZX-1711 (naphthalene diphenolic epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epotohto ESN -155 (beta-naphthol aralkyl epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), Epotohto ESN-355, Epotohto ESN-375 (Ninatron Sumikin Chemical Co., Ltd. bisphthol aralkyl Epoxy resin), Epotohto ESN-475V, Epotohto ESN-485 (α-naphthol aralkyl epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.) Phenyl Methane type epoxy resin), Sumiepoxy TMH-574 (Sumitomo Chemical Co., Ltd. phenylene glycol type epoxy resin), YSLV-120TE (Nissinzu Sumiyuki Chemical Co., Ltd. disulfide type epoxy resin), Epotohto ZX-1684 (Nippon Steel & Sumitomo Chemical Co., Ltd. resorcinol type epoxy resin), Epiclon HP-7200H (dicyclopentadiene type epoxy resin manufactured by DIC Corporation), TX-0929, TX -0934, TX-1032 (Nippon Steel & Sumitomo Chemical Co., Ltd.), Celoxide 2021 (aliphatic epoxy resin manufactured by DAICEL Chemical Industry Co., Ltd.), Epotohto YH-434 ( Nippon Steel Sumikin Chemical Co., Ltd. produces diaminodiphenylmethane tetraglycidylamine), jER 630 (amino phenolic epoxy resin manufactured by Mitsubishi Chemical Corporation), Epotohto EX-289B, Epotohto FX-305 , TX-0932A (a phosphorus-containing epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), an amine urethane modified epoxy resin, an epoxy resin containing an oxazolidinone ring, etc., but is not limited thereto Wait. Further, these epoxy resins may be used singly or in combination of two or more kinds.

In the epoxy resin composition of the present invention, the phenol compound (B) represented by the above formula (1) must be used as a curing agent component, but other epoxy resins may be used in combination without impairing the object of the present invention. Resin hardener.

Specific examples of the epoxy resin hardener which can be used in combination include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol S, bisphenol Z, bisphenol quinone, and the like. Tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl-6 -T-butylphenol), 4,4'-biphenol, 3,3'-5,5'-tetramethyl-4,4'-dihydroxybiphenyl, catechol, isophthalic acid Phenol, methyl resorcinol, hydroquinone, monomethyl hydroquinone, dimethyl hydroquinone, trimethyl hydroquinone, mono-tertiary-butyl hydroquinone Divalent phenols such as di-tertiary-butyl hydroquinone, dihydroxynaphthalene, dimethylol naphthalene, trishydroxynaphthalene, ginseng-(4-hydroxyphenyl)methane, 1,1,2 a trivalent or higher phenol such as 2-anthracene (4-hydroxyphenyl)ethane, a phenol novolak or an o-cresol novolak, or a co-condensation phenol derived from dicyclopentadiene and a phenol. a condensed phenol derived from a phenol, a formaldehyde, and an alkoxy group, and a phenol aralkyl phenol obtained from a phenol and p-Xylenedichloride. a phenol such as a biphenyl aralkyl group obtained from a phenol or a bischloromethylbiphenyl group, a naphthol aralkyl group obtained from a naphthol or a paraphthylene dichloride, and the like. . Other epoxy resin hardeners include, for example, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Pyrormellitic anhydride, phthalic anhydride, Trimellitic anhydride, and methyl group. Anhydride such as Methylnadic Anhydride, diethylenetriamine, triethylenetetramine, m-xylylenediamine, isophoronediamine, diaminediphenylmethane, diaminediphenylphosphonium (diamine) Triaminophosphine, such as diaminodiphenyl sulfone), an amine compound such as a polyamine condensate of an acid such as diamine diphenyl ether, dicyandiamide or a dimer acid, and a polyamine. a phosphonium compound, a phosphonium salt such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl Imidazoles such as -2-methylimidazole and their salts with imidazole salts, trimeric cyanuric acid, boron, etc., imidazolium salts, benzyldimethylamine, 2,4,6-para (second An amine such as methylaminomethyl)phenol, a 4-grade ammonium salt such as trimethylammonium chloride, or a diazide A ring compound, a salt thereof such as a phenol or a phenol novolak resin, a compound such as boron trifluoride, an amine or an ether compound, an aromatic hydrazine or an oxonium salt.

These epoxy resins may be used singly or in combination of two or more kinds. The blending amount of these may be within the range not impairing the object of the present invention, but is based on the total amount of the phenol compound (B) represented by the formula (1) and other epoxy resin hardeners. The amount is less than 50% by mass, more preferably less than 40% by mass, and even more preferably less than 25% by mass.

Further, in the epoxy resin composition of the present invention, the epoxy resin hardener is blended in an amount of 1 mol based on the epoxy group (A), and the epoxy resin hardener containing the phenol compound (B). The active hydrogen group is preferably in the range of 0.4 to 1.2 mol, more preferably 0.5 to 1.1 mol, and still more preferably 0.7 to 1.0 mol. Too little or too much of the epoxy resin hardener relative to the epoxy group may cause incomplete hardening and may not provide good hardenability. Further, the active hydrogen group of the epoxy resin curing agent means a functional group reactive with an epoxy group, and specific examples thereof include a phenolic hydroxyl group, an amine group, and a carboxyl group.

A hardening accelerator can be used as needed in the epoxy resin composition of the present invention. Specific examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and 2-(dimethylaminomethylmethyl). a third-grade amine such as phenol, 1,8-diaza-bicyclo(5,4,0)undec-7-ene, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine A metal compound such as a phosphine such as triphenylborane or tin octylate. The hardening accelerator may be used alone or in combination of two or more. Hardening accelerator is relative to the hair 100 parts by mass of the epoxy resin (A) in the epoxy resin composition of the present invention is used in an amount of 0.02 to 5.0 parts by mass as needed. By selectively using such a hardening accelerator, the hardening temperature can be lowered and the hardening time can be shortened.

In the epoxy resin composition of the present invention, an organic solvent may be used as the viscosity adjustment, and an organic solvent which can be used is not particularly limited. However, specific examples thereof include N,N-dimethylformamidine. An amine such as an amine or an ether such as ethylene glycol monomethyl ether; a ketone such as acetone or methyl ketone; an alcohol such as methanol or ethanol; or an aromatic hydrocarbon such as benzene or toluene. These solvents may be used singly or in combination of two or more.

The epoxy resin composition of the present invention may be formulated with a curable resin or a thermoplastic resin other than the epoxy resin within a range that does not impair the properties. Specific examples thereof include a phenol resin, an acrylic resin, a petroleum resin, an Indene resin, an Indene-coumarone resin, a phenoxy resin, a cyanate resin, and an epoxy acrylate. Resin, vinyl compound, polyurethane, polyester, polyamine, polyimide, polyamidimide, polyetherimide, bismaleimide-triazine resin ), polyether oxime, polyfluorene, polyetheretherketone, polyphenylene sulfide, polyvinylvinyl formal, but not limited by these.

A filler may be used as needed in the epoxy resin composition of the present invention. Specific examples thereof include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, fired talc, clay, kaolinite, titanium hydroxide, glass frit, and sulphur dioxide hollow particles (Silica balloon), but may be formulated. Organic or inorganic moisture-resistant pigments, flaky pigments, and the like. Use general inorganic filler For the reason, the impact resistance can be improved. Further, a fibrous filler such as glass fiber, pulp fiber, synthetic fiber or ceramic fiber, or an organic filler such as fine particle rubber or thermoplastic elastomer may be used.

Further, the epoxy resin composition of the present invention may be formulated with additives such as a flame retardant, a rheologically modified material, and a fluidity promoter as needed. The rheologically modified material may, for example, be a polyoxyxene system, a castor oil system, an aliphatic polyamidamide wax, an oxidized polyethylene wax, or an organic bentonite system. Further, if necessary, the resin composition of the present invention may be formulated with 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 a low stress such as polyfluorene oxide oil. Lubricants, calcium stearate and other lubricants.

Next, the prepreg obtained by using the epoxy resin composition of the present invention will be described. As the sheet-like substrate, an inorganic fiber such as glass or a woven or non-woven fabric of an organic fiber such as polyester, polyacryl, polyacryl, polyimine or Kevlar may be used, but it is not limited thereto. The epoxy resin composition of the present invention and the method for producing the prepreg from the substrate are not particularly limited. For example, the above-mentioned substrate is immersed in a resin varnish after the viscosity adjustment of the epoxy resin composition described above in a solvent (Varnish) After the impregnation, the resin component is semi-cured (B-staged) by heating and drying, for example, it can be dried by heating 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 based on the resin.

Next, the back sheet obtained by using the epoxy resin composition of the present invention will be described. The method for producing the adhesive sheet is not particularly limited, but is not dissolved in the epoxy resin such as a polyester film or a polyimide film. On the carrier film of the composition, the epoxy resin composition of the present invention is preferably applied to a thickness of 5 to 100 μm, and then dried by heating at 100 to 200 ° C for 1 to 40 minutes to form a sheet. A method generally known as a casting method to form a resin sheet. If the sheet coated with the epoxy resin composition is previously subjected to a surface treatment with a release agent, the formed back sheet can be easily peeled off. Here, the thickness of the succeeding sheet is desirably formed to be 5 to 80 μm. The adhesive sheet obtained by such a method is generally an insulating back sheet having an insulation, but a conductive adhesive sheet can be obtained by mixing a conductive metal or a metal-coated fine particle in an epoxy resin composition.

Further, a method of producing a laminate using the prepreg of the present invention or an insulating back sheet will be described. When a prepreg is used to form a laminate, the prepreg is laminated in one or a plurality of layers, and a metal foil is placed on one side or both sides to form a laminate. The laminate is heated and pressurized to be integrated. Here, as the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel may be used. The heating and pressing conditions of the laminate are appropriately adjusted by heating and pressing the epoxy resin composition. However, if the pressure is too low, bubbles may remain in the interior of the obtained laminate. Since the electrical characteristics are lowered, it is preferable to pressurize under the conditions of moldability. For example, the temperature may be set to 160 to 220 ° C, the pressure may be 49.0 to 490.3 N/cm ² (5 to 50 kgf/cm ² ), and the heating time may be 40 to 240 minutes. Further, 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, first, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is treated with an acid solution to be blackened to obtain an inner layer. The circuit forming surface on one side or both sides of the inner layer is formed of a prepreg or an insulating back sheet to form an insulating layer while forming a conductor layer on the surface of the insulating layer to form a multilayer board. When the insulating layer is formed by insulating the adhesive sheet, an insulating film is placed on the circuit forming surface of the inner layer of the plurality of sheets to form a laminate. Or an insulating back sheet is disposed between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, it is integrally molded by heating and pressing the laminate to form a cured product of the insulating back sheet as an insulating layer, and at the same time, multilayering of the inner layer material is formed. A metal foil in which an inner layer material and a conductor layer are formed by using a cured product of an insulating back sheet as an insulating layer. Here, the metal foil can be the same as the user of the laminate used for the inner layer. Further, the heat and pressure forming system can be carried out under the same conditions as the molding of the inner layer. When the epoxy resin composition is coated on the laminate to form an insulating layer, the circuit-forming surface resin of the outermost layer of the inner layer material is coated with the epoxy resin composition at a thickness of preferably 5 to 100 μm, and is 100 to 200. Dry at °C for 1 to 90 minutes to form a flake. It is generally formed by a method called casting. The thickness after drying is preferably formed to be 5 to 80 μm. On the surface of the multi-layered laminate formed by such a method, a Via hole or a circuit can be formed by an addition or subtraction method to form a printed wiring board. Further, by repeating the above-described method by using the printed wiring board as an inner layer material, it is possible to form a multilayer laminated board. When the insulating layer is formed of the prepreg, one or a plurality of laminated prepregs are placed on the circuit forming surface of the inner layer, and a metal foil is further disposed on the outer side to form a laminate. Then, the laminate is heated and pressed to be integrally molded to form a cured product of the prepreg as an insulating layer, and the outer metal foil is used as a conductor layer. Here, the metal foil may be the same as the user of the laminate used as the inner layer. Further, the heat and pressure forming system can be carried out under the same conditions as the molding of the inner layer. On the surface of the multilayered laminate formed by such a method, a via hole or a circuit can be formed by an addition or subtraction method to form a printed wiring board. Further, by repeating the above-described method by using the printed wiring board as an inner layer material, a multilayer laminated board can be further formed.

Further, when the epoxy resin composition of the present invention is heat-cured, an epoxy resin cured product can be formed, and the cured product is excellent in low dielectric properties, heat resistance, low moisture absorption, and the like. The cured product can be obtained by molding an epoxy resin composition by casting, compression formation, transfer formation or the like. 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, the adhesive sheet, the laminate, the encapsulant, the cast, and the cured product obtained by using the composition are excellent in low dielectric properties, heat resistance, and low hygroscopicity. And those who show excellent characteristics in the next.

(Example)

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

(1) Determination of epoxy equivalent

Measured according to JIS K7236 specifications. Specifically, a potentiometric titration apparatus was used, and methyl ethyl ketone was used as a solvent, and a tetraethylammonium bromide acetic acid solution was added thereto, and a 0.1 mol/L perchloric acid-acetic acid solution was used.

(2) Determination of phosphorus content

Add sulfuric acid, hydrochloric acid, perchloric acid to the sample, heat and wet ashing, All phosphorus atoms are considered to be orthophosphoric acid. The metavanadate and the molybdate were reacted in an acidic sulfuric acid solution, and the absorbance of the resulting Phospho vanado molybdate acid complex at 420 nm was measured, and the phosphorus atom content was expressed in %. Further, a B-stage resin powder was used for the sample for measuring the epoxy resin composition.

(3) Determination of phenolic hydroxyl equivalents

To the sample, 4% methanolic THF and 10% tetrabutylammonium hydroxide were added, and the absorbance at a wavelength between 400 nm and 250 nm was measured by an ultraviolet-visible spectrophotometer to determine a phenolic hydroxyl group as a hydroxyl group. The number of g of the sample.

(4) Determination of water absorption rate

According to JIS C 6481, the measurement was carried out according to the change in weight after immersion in water at 23 ° C for 24 hours.

(5) Determination of specific dielectric ratio and dissipation factor

The value of 1 GHz was measured by a cavity network resonance method (VNA E8363B (manufactured by Agilent Technologies), and a cavity evoked dielectric constant rate measuring device (manufactured by Kanto Electronics Co., Ltd.).

(6) Determination of the force

According to JIS K 6854-1, an automatic mapper (Autograph) manufactured by Shimadzu Corporation was used at 50 mm/min in an environment of 25 °C.

(7) Determination of water resistance

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

(8) T-288 test

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

(9) Determination of glass transition temperature

It was measured in accordance with JIS K 7121 Differential Scanning Calorimetry. By using EXTER DSC6200 manufactured by SII Co., Ltd., the temperature was measured at a temperature increase rate of 10 ° C /min from 20 ° C, and the glass transition start temperature (Tig) of the DSC chart obtained in the second cycle was determined.

(10) Determination of flame retardancy

The copper foil portion was immersed in an etching solution to remove the copper foil portion, and after washing and drying, a test piece having a cut length of 127 mm and a width of 12.7 mm was used, and tested according to UL94 (Underwriters Laboratories Inc. safety certification specification). The method (V method) is ignited to measure the burning time. The evaluation was recorded in V-0, V-1, and V-2. However, the complete burner was recorded as "burning."

Synthesis Example 1 (Synthesis of Phenol Compound (B1))

In a 4-neck glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 806 parts of methanol and 201.7 parts of potassium hydroxide were added, followed by stirring, and then double (di) as a dihydroxy compound (a) was added thereto. 550 parts of 4-hydroxy-3,5-dimethylphenyl)anthracene (hereinafter, TMBPS) forms an alkali metal salt. Thereafter, 4.5 parts of 4,4'-bischloromethylbiphenyl (hereinafter, BCMB) as a halogenated methyl group-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 carried out for 2 hours.

After the reaction is completed, the salt formed is removed by filtration at 50 mmHg. The temperature was raised to 100 ° C under reduced pressure, and methanol and bis(2-methoxyethyl)ether were distilled off, and then 1290 parts of toluene was added and dissolved. After neutralizing the mixture with phosphoric acid, the mixture was further washed twice with water, and then toluene was evaporated to give 526 parts of 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))

367 parts of methanol and 91.7 parts of potassium hydroxide were added to a four-neck glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and then 250 parts of TMBPS as a dihydroxy compound (a) was added. Forming 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 charged, and the mixture was heated to 75 ° C while stirring, and reacted for 2 hours.

After the completion of the reaction, the salt formed was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg. The total amount of methanol and bis(2-methoxyethyl)ether was distilled off, and then 685 parts of toluene was added to dissolve. After neutralizing the mixture with phosphoric acid, the mixture was further washed twice with water, and then toluene was evaporated to give 279 parts of 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))

To a 4-neck glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 323 parts of methanol and 80.7 parts of potassium hydroxide were added, stirred, and TMBPS 220 as a dihydroxy compound (a) was further added. Parts form an alkali metal salt. Thereafter, 690.2 parts of BCMB as a compound (b) containing a halogenated methyl group and bis(2-methoxyethyl) ether 401 as a solvent were added. The mixture was heated to 75 ° C while stirring, and reacted for 2 hours.

After completion of the reaction, the salt formed was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg, and methanol and bis(2-methoxyethyl)ether were distilled off, and then 663 parts of toluene was added and dissolved. After the mixture was neutralized with phosphoric acid, the mixture was further washed twice with water, and then 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))

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

After completion of the reaction, the salt formed was removed by filtration, and the temperature was raised to 100 ° C under reduced pressure of 50 mmHg. After methanol and bis(2-methoxyethyl)ether were distilled off, 657 parts of toluene was added and dissolved. After the mixture was neutralized with phosphoric acid, the mixture was further washed 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))

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

After completion of the reaction, the salt formed was removed by filtration, and the temperature was raised to 100 ° C under reduced pressure of 50 mmHg. After methanol and bis(2-methoxyethyl)ether were distilled off, 670 parts of toluene was added and dissolved. After the mixture was neutralized with phosphoric acid, the mixture was further washed twice with water, and then toluene was evaporated to yield 230 parts of 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-neck glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 293 parts of methanol and 73.3 parts of potassium hydroxide were added, and 200 parts of TMBPS as a dihydroxy compound (a) was added. An alkali metal salt is formed. Thereafter, 57.2 parts of dichloromethylbenzene (P-xylyl dichloride; PXDC) as a compound (b) containing a halogenated methyl group 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 carried out for 2 hours.

After completion of the reaction, the salt formed was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg, and methanol and bis(2-methoxyethyl)ether were distilled off, and then 544 parts of toluene was added and dissolved. After the mixture was neutralized with phosphoric acid, the mixture was further washed twice with water, and then toluene was evaporated to yield 215 parts of 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 Phenolic Compound (B7))

In a 4-port glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 438 parts of methanol and 109.6 parts of potassium hydroxide were added, and then tetramethyl bis(di) as a dihydroxy compound (a) was added. Phenol F (hereinafter, TMBPF) was 250 parts to form an alkali metal salt. Thereafter, 51.2 parts of PXDC as a compound (b) containing a halogenated methyl group and 265 parts of bis(2-methoxyethyl)ether as a solvent were added, and the mixture was heated to 75 ° C while stirring, and reacted for 2 hours.

After completion of the reaction, the salt formed was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg, and methanol and bis(2-methoxyethyl)ether were distilled off, and then 653 parts of toluene was added and dissolved. After the mixture was neutralized with phosphoric acid, the mixture was further washed 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 Phenolic Compound (B8))

In a 4-neck glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 257 parts of methanol and 64.1 parts of potassium hydroxide were added, and then bisphenol quinone (di) was added as a dihydroxy compound (a). Hereinafter, 200 parts of BPFL) forms an alkali metal salt. Thereafter, 71.7 parts of BCMB as a compound (b) containing a halogenated methyl group and 378 parts of bis(2-methoxyethyl)ether as a solvent were added, and the mixture was heated to 75 ° C while stirring, and reacted for 2 hours.

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

Synthesis Example 9 (Synthesis of Phenolic Compound (B9))

In a 4-neck glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 219 parts of methanol and 54.8 parts of potassium hydroxide were added, and then TMBPF 125 parts as a dihydroxy compound (a) was added. Forming an alkali metal salt. Thereafter, 55 parts of 1,5-dichloromethylnaphthalene (hereinafter BCMN) as a compound (b) containing a halogenated methyl group 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 salt formed was removed by filtration, and the temperature was raised to 100 ° C under a reduced pressure of 50 mmHg, and methanol and bis(2-methoxyethyl)ether were distilled off, and then 393 parts of toluene was added and dissolved. After the mixture was neutralized with phosphoric acid, the mixture was further washed twice with water, and then toluene was evaporated to afford 142 g of 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))

In a four-port glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, YDPN-638 (Nippon Steel & Sumitomo Chemical Co., Ltd., phenol novolak type epoxy resin, Epoxide equivalent = 177 g / eq) 359 parts and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA: Sanguang Co., Ltd.) 141 parts were reacted at 160 ° C for 4 hours. A phosphorus-containing epoxy resin (A2) was obtained. The obtained epoxy resin had an epoxy equivalent of 370 g/eq and a phosphorus content of 4.0%.

Synthesis Example 11 (Synthesis of Epoxy Resin (A6))

Into a three-port glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 67 parts of HCA, 48 parts of 1,4-naphthoquinone, and 142 parts of toluene were added and stirred at 75 ° C for 30 minutes, and then After dehydration at 110 ° C for 90 minutes, 518 parts of ESN-485 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., naphthol aralkyl type epoxy resin, epoxy equivalent = 296 g / eq) was added, and then the temperature was raised to remove toluene. Thereafter, 0.01 part of triphenylphosphine (TPP) as a catalyst was added, and the mixture was 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 four-port glass separation flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 70 parts of HCA, 25 parts of 1,4-naphthoquinone, and 148 parts of toluene were added and stirred at 75 ° C for 30 minutes, and then After dehydration reaction at 110 ° C for 90 minutes, 540 parts of NC-7700 (manufactured by Nippon Kayaku Co., Ltd., β-naphthol cresol condensation type epoxy resin, epoxy equivalent = 222 g/eq) was added, and then toluene was removed by heating. Thereafter, 0.01 part of TPP as a catalyst was added, and the mixture was reacted at 160 ° C for 4 hours to obtain a 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, the hardener, and the hardening accelerator used in the examples and the comparative examples 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 type 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 = 3.0%)

(A5): TX-1106B (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., phosphorus-containing epoxy resin, epoxy equivalent = 385 g/eq, phosphorus content = 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): phenolic 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): Shonol BRG-557 (manufactured by Showa Denko Co., Ltd., phenol novolac resin, phenolic hydroxyl equivalent = 105 g/eq, softening point = 86 ° C)

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

(B12): dicyandiamide (DICY, active hydrogen equivalent = 21 g/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 heated in a hydroxy-heated epoxy resin (A) while heating the curing agent (B) to 120 ° C, and homogenized to obtain an epoxy resin composition. The obtained epoxy resin composition was defoamed under reduced pressure at the same temperature, and then hardened by adding a hardening accelerator to make it uniform to avoid generation of bubbles, and was cast in a mold, and hardened at 150 ° C for 2 hours in a hot air circulating oven. Subsequently, it was hardened at 180 ° C for 3 hours to obtain a cured product. The evaluation results of the obtained cast cured product are shown in Table 1.

Examples 13 to 18 and Comparative Examples 3 to 8

According to the formula shown in Table 2, epoxy resin (A), hardener (B), A hardening accelerator and a solvent are used 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 are used by being dissolved in methyl ethyl ketone (MEK) in advance. The glass cloth (manufactured by Nittobra Co., Ltd., IPC specification 2116) was impregnated with the obtained epoxy resin composition varnish, and then impregnated in a hot air circulating oven at 150 ° C for 7 minutes to obtain a B-stage preheating. Dip. One of the obtained prepregs was used for layer formation, and four sheets of overlapping prepregs were overlapped with copper foil (3EC-III, 35 μm thick manufactured by Mitsui Mining Co., Ltd.) at 130 ° C for X15 minutes + 190 ° C. A vacuum of 2 MPa was performed under a temperature condition of X80 minutes to obtain a laminated plate having a thickness of 0.5 mm. The other is for the measurement of dielectric properties, and the purpose is to form a cured resin alone, using about 10 g of B-stage resin powder obtained by pulverizing several prepregs, and using the same Teflon frame mold and the same vacuum stamping. The hardened condition gave a resin plate of 2 mm thick. The evaluation results of the molded articles obtained in these are shown in Table 2.

(industrial availability)

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

Claims (8)

An epoxy resin composition comprising an epoxy resin (A) and a phenol compound (B) represented by the formula (1); Wherein m is the number of repeating units, and the average value is 0 < m < 10, and X and Y are selected from a phenyl group, an extended naphthyl group or a general formula which may have a hydrocarbon group having a carbon number of 1 to 10 or a halogen atom as a substituent. (2) at least one of the groups represented by the same 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; and R ₂ is a single bond or a divalent group. The epoxy resin composition according to the first aspect of the invention, wherein the phenol compound (B) is the same as the dihydroxy compound (a) represented by the following formula (3): a phenol compound (B) obtained by reacting a halogenated methyl group-containing compound (b) represented by the formula (4) in a range of 0.001 to 1.0 mol; in the formula HO-Y-OH (3) , Y is selected from a phenyl group having a carbon number of 1 to 10 or a halogen atom as a substituent, or a naphthyl group or at least one group represented by the formula (2); Z-CH ₂ -X-CH ₂ -Z ( In the formula 4) , X is at least one selected from the group consisting of a stretching phenyl group, a stretching 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; Halogen atom; 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; and R ₂ is a single bond or a divalent group. The epoxy resin composition according to claim 1, wherein the epoxy resin (A) is a phosphorus-containing epoxy resin containing 50 to 100% by mass, and the phosphorus-containing epoxy resin has 0.5 Phosphorus content to 6.0% by mass. The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy group containing 1 mol of the epoxy resin (A) contains a ring of the phenol compound (B). The active hydrogen group of the oxy-resin hardener is in the range of 0.4 to 1.2 mol. A prepreg characterized by using the epoxy resin composition according to any one of claims 1 to 4. An adhesive sheet characterized by using the epoxy resin composition according to any one of claims 1 to 4. An epoxy resin laminate comprising the epoxy resin composition according to any one of claims 1 to 4. A cured product obtained by hardening an epoxy resin composition according to any one of claims 1 to 4 of the patent application.