KR102230098B1 - Epoxy resin composition and cured product thereof - Google Patents

Abstract

(식 중, m 은 반복수이고, 평균치는 0 < m < 10 이다. X, Y 는 치환기로서 탄소수 1 ∼ 10 의 탄화수소기 또는 할로겐 원자를 가져도 되는 페닐렌기, 나프틸렌기 또는 일반식 (2) 로 나타내는 기에서 선택되는 적어도 1 종의 기이고, 동일해도 되고 상이해도 된다.)
[화학식 2]

(식 중, R₁ 은 수소 원자, 탄소수 1 ∼ 10 의 탄화수소기 또는 할로겐 원자이고, 서로 동일해도 되고 상이해도 된다. R₂ 는 단결합 또는 2 가의 기이다.) (Problem) The present invention provides an epoxy resin composition having excellent performance in low dielectric properties and high heat resistance, and useful for applications such as lamination, molding, molding, bonding, and the like, and a cured product thereof.
(Solving means) It is an epoxy resin composition containing an epoxy resin (A) and a curing agent (B) represented by General Formula (1), and a cured product thereof.
[Formula 1]

(In the formula, m is a repeating number, and the average value is 0 <m <10. X and Y are a phenylene group, a naphthylene group, or a general formula (2) which may have a hydrocarbon group having 1 to 10 carbon atoms as a substituent or a halogen atom. It is at least 1 type of group selected from the group represented by ), and may be the same or different.)
[Formula 2]

(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 as or different from each other. R ₂ is a single bond or a divalent group.)

Description

Epoxy resin composition and cured product thereof {EPOXY RESIN COMPOSITION AND CURED PRODUCT THEREOF}

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

BACKGROUND ART In recent years, the demand for small-sized mobile communication devices, such as smartphones and tablet PCs, which have become personal communication terminals is rapidly growing. Along with this, the signal band of the information and communication device and the CPU frequency of the computer have reached the GHz band, and higher frequencies are being promoted.

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

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

Epoxy resin is a representative insulating material used in the above communication devices, but, of course, even for printed laminates, the required performance is low in dielectric constant and dielectric loss tangent, so that basic performances such as heat resistance and adhesion are provided as in the prior art. Is required. In addition, in recent years, halogen-free flame retardancy has been established as an environmental response.

As a halogen-free flame-retardant method, many methods have been reported in which 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO), which is a reactive phosphorus compound, is reacted with an epoxy group. In this method, there is a problem in that the crosslinking density of the cured product is lowered and heat resistance is deteriorated because the need to increase the phosphorus content rate in order to increase the expression of flame retardancy results in a decrease in the number of epoxy groups contained in one molecule.

Regarding this problem, improvement of increasing the crosslinking density by using a polyfunctional epoxy resin and a polyfunctional curing agent is generally attempted, but the cured product is hard and broken, thereby lowering the good adhesion of the epoxy resin, and at the same time, Since the concentration of hydroxyl groups generated in the cured product accompanying the curing reaction also increases, there has been a serious problem that causes deterioration of dielectric properties.

In short, this means that there is no material that satisfies the properties such as reduction of dielectric properties that are contrary to the required performance improvement such as heat resistance, flame retardancy, and adhesion, and it is a very difficult task to solve in the conventional design concept of epoxy resin and curing agent. .

For such a difficult problem, there have been many reports of techniques in which improvement is achieved by a method in which a cyanate ester compound is used in combination with an epoxy resin and its curing agent system. These materials are effective in improving the dielectric properties, but with an increase in the amount used, the cured product becomes hard and it is difficult to sufficiently satisfy any of adhesiveness, flame retardancy, and processing workability (Patent Document 2).

As another low-dielectric material, many methods have been reported in which a modified phenol compound obtained by reacting a polyphenyl ether resin with a phenolic compound is used in combination with an epoxy resin. The modified phenolic material, which is a material for imparting low dielectric properties, inevitably increases its molecular weight due to repolymerization accompanying decomposition at the time of its synthesis, resulting in a decrease in workability such as impregnation into the glass cloth, and the raw material is expensive. Also in that regard, it is not very suitable for development to a general purpose communication terminal device application (Patent Document 3).

Japanese Patent Publication No. 2012-221968 Japanese Unexamined Patent Application Publication No. Hei 06-248074 Japanese Patent Laid-Open Publication No. Hei 10-273518

Accordingly, the problem to be solved by the present invention is to provide an epoxy resin composition and a cured product thereof that have excellent performance in low dielectric properties and high heat resistance, and are useful for applications such as lamination, molding, molding, and bonding.

That is, this invention is an epoxy resin composition containing an epoxy resin (A) and a phenol compound (B) represented by general formula (1).

[Formula 1]

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

[Formula 2]

(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 as or different from each other. R ₂ is a single bond or a divalent group.)

In addition, the phenol compound (B) is 0.001 to 1.0 mol of the halogenated methyl group-containing compound (b) represented by the following general formula (4) with respect to 1 mol of the dihydroxy compound (a) represented by the following general formula (3). It is preferable that it is a phenol compound obtained by making it react in the range of.

[Formula 3]

(In the formula, Y is at least one group selected from a hydrocarbon group having 1 to 10 carbon atoms as a substituent or a phenylene group, a naphthylene group, or a group represented by the general formula (2) which may have a halogen atom.)

[Formula 4]

(In the formula, X is at least one group selected from a hydrocarbon group having 1 to 10 carbon atoms as a substituent or a phenylene group, a naphthylene group, or a group represented by the general formula (2) which may have a halogen atom. Z is a halogen Represents an atom.)

[Formula 5]

(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 as or different from each other. R ₂ is a single bond or a divalent group.)

Moreover, it is preferable that the said epoxy resin (A) contains the phosphorus containing epoxy resin which is 0.5 to 6.0 mass% of phosphorus content in the range of 50 to 100 mass %.

Moreover, it is preferable that the active hydrogen groups of the epoxy resin curing agent containing the phenol compound (B) are in the range of 0.4 to 1.2 moles per 1 mole of the epoxy group of the epoxy resin (A).

In addition, the present invention is a prepreg obtained from the above epoxy resin composition, an adhesive sheet, an epoxy resin laminate, an epoxy resin encapsulant, and an epoxy resin mold. In addition, the present invention is a cured product obtained by curing the above epoxy resin composition.

The epoxy resin composition of the present invention can be preferably used for applications such as lamination, molding, molding, bonding, etc., by imparting a cured product excellent in low dielectric properties and high heat resistance.

The epoxy resin composition of the present invention has an epoxy resin (A) and a phenol compound (B) represented by General Formula (1) as essential components.

In the phenol compound (B) represented by the general formula (1), m is a repeating number, and the average value is required to be 0 <m <10, preferably 0.01 <m <8, more preferably 0.05 <m <5. When m = 0, that is, when the phenol compound (B) represented by the general formula (1) is not contained, there is no effect on the low dielectric property, and when m is large, there is a fear of high viscosity. When m is an average value in the range of 0 <m <10, the viscosity is not high, and the effect of low dielectric properties can be expressed. In addition, the phenolic hydroxyl group equivalent is not particularly defined, but 1000 g/eq or less is preferable, and 500 g/eq or less is more preferable. When the phenolic hydroxyl group equivalent is large, the molecular weight increases, so that the viscosity becomes high, and there is a fear that the heat resistance of the cured product decreases. Here, the average value is a number average.

In addition, X and Y in the general formula (1) are at least one member selected from a phenylene group, a naphthylene group, or a group represented by general formula (2) which may have a substituent, and may be the same or different. In the case of having a substituent, the substituent is a C1-C10 hydrocarbon group or a halogen atom, and specific examples of these hydrocarbon groups and halogen atoms include those similar to _{R 1 in General Formula (2) described later.}

In 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 as or different from each other. Specific examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n -C1-C10 linear or branched alkyl groups such as hexyl groups, cyclic alkyl groups having 4-10 carbon atoms such as cyclohexyl groups, phenyl groups, naphthyl groups, tolyl groups, xylyl groups, indanyl groups, etc. Aryl groups which may have 10 substituents, benzyl group, phenethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2,6-dimethylbenzyl group, 3,5-dimethylbenzyl group, Substituents such as an aralkyl group which may have a substituent having 7 to 10 carbon atoms such as an α-methylbenzyl group, and the like. Preferable substituents are methyl, ethyl, tert-butyl, cyclohexyl, phenyl, α-methylbenzyl to be.

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 divalent groups include -CH ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₃ )-, -C(CF ₃ ) ₂ -, -CO-, -O-, -S- , -SO ₂ -, benzylidene group, α-methylbenzylidene group, cyclohexylidene group, cyclopentylidene group, 9H-fluorene-9-ylidene group, or cyclohexenyl group, and the like. The aromatic skeleton of may further have a substituent having the same meaning _{as R 1.} Preferred divalent groups are -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, -S-, -SO ₂ -, 9H-fluorene-9-ylidene group.

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

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

Conventionally, polyether synthesis by reaction with a halide using a hydroxyl group as an alkali metal salt has been known, and in the reaction of a dihydroxy compound (a) and a halogenated methyl group-containing compound (b) to obtain a phenol compound (B), this polyether Ether synthesis method can be used. Further, 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), and m increases as the molar ratio is closer to 1. However, the (a)/(b) ratio is greater than 1 in that both ends need to be hydroxy groups.

In addition, when it is desired to further impart heat resistance, a small amount of a trifunctional or higher hydroxy compound is used in combination to produce an effect. However, since the cured product becomes highly elastic, the degree of not affecting the adhesion is allowed.

When a dihydroxy compound (a) is specifically illustrated, dihydroxy compounds containing phenylene groups such as hydroquinone, resorcin, and catechol, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 Naphthalenediols such as ,6-dihydroxynaphthalene, bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, 4,4'-oxybisphenol, 4,4'-carbonylbisphenol , Bisphenol fluorene, 4,4'-biphenol, 2,2'-biphenol, bisphenol acetophenone, and other divalent phenols, and carbon number 1 having the same meaning as _{R 1 in the general formula (2).} These compounds, etc. which have a hydrocarbon group of -10 or a halogen atom as a substituent are mentioned. Preferably, 4-hexylresorcinol, 1,6-dihydroxynaphthalene, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbiphenol, 4,4'-oxybisphenol, 4, 4'-carbonylbisphenol, bisphenolfluorene, and tetrabromobisphenol A are mentioned, More preferably, tetramethylbisphenol S, bisphenolfluorene, and tetrabromobisphenol A are mentioned.

Specific examples of the halogenated methyl group-containing compound (b) are bischloromethylbenzene, bischloromethylnaphthalene, bischloromethylbiphenyl, bischloromethylfluorene, and the like, and have the same meaning as _{R 1 in the general formula (2).} These compounds which have a C1-C10 hydrocarbon group or a halogen atom are mentioned.

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 methyl halide group-containing compound (b) in the range of 0.001 to 1.0 moles with respect to 1.0 moles of the dihydroxy compound (a), the preferable range is 0.01 to 0.9 moles, and the more preferable range is 0.05. It is -0.8 mol, and a more preferable range is 0.1-0.7 mol. When the amount of the methyl halide group-containing compound (b) is 1 mol or more, the phenol compound (B) represented by the general formula (1) cannot be obtained because the terminal group of the reaction product becomes halogen.

The reaction of the dihydroxy compound (a) with the methyl halide group-containing compound (b) can be carried out in the presence of an alkali metal hydroxide such as potassium carbonate, sodium hydroxide, and potassium hydroxide, and the reaction temperature is 20 to 100°C, preferably Is 50 to 60°C, and the reaction time is 1 to 10 hours. At 20°C or lower, the reaction does not proceed, and at 100°C or higher, an electrophilic substitution reaction may occur.

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 preferably has an average of 2 to 6 epoxy groups in the molecule, and has an average of 2.5 to 5 epoxy groups in the molecule. It is more preferable, and it is still more preferable to have an average of about 3 to 4 epoxy groups in the molecule. Particularly preferably, it is a novolak type epoxy resin. If there are few epoxy groups, there is a concern that the heat resistance of the cured product may be adversely affected, and if there are many epoxy groups, there is a concern that the adhesiveness is adversely affected.

Moreover, when flame retardancy is required by halogen-free, it is preferable to contain 50-100 mass% of phosphorus containing epoxy resin which is 0.5-6.0 mass% of phosphorus content. In the case where the phosphorus content is small, even if a skeleton having high flame retardancy is introduced into the phenolic compound (B) of the present invention or a filler or a flame retardant auxiliary agent is used, sufficient flame retardancy may not be exhibited. Further, when the phosphorus content is large, the flame retardancy can be sufficiently exhibited, but the resin composition has a high viscosity, and there is a concern that the solvent solubility and water resistance may deteriorate. In addition, when DOPO is used as a phosphorus feedstock, the softening point of the epoxy resin (A) is also very high, the workability such as melting or impregnation and molding decreases, and the molecular weight of the epoxy resin (A) itself increases, and the phenol compound Since the reactivity with (B) also falls, there exists a possibility that the effect of heat resistance as a hardened|cured material, adhesiveness, and dielectric properties may not be exhibited. Therefore, it is preferable to control the phosphorus content rate in the range of 0.5 to 6.0 mass %, the range of 1.0 to 5.0 mass% is more preferable, and the range of 2.0 to 4.0 mass% is still more preferable.

Specific examples of the epoxy resin (A) include Epotot YD-128, Epotot YD-8125, Epotot YD-825GS (Bisphenol A type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), and Epotot YDF- 170, Ephotote YDF-170B, Ephotote YDF-8170, YDF-870GS (Bisphenol F type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), YSLV-80XY (Tetramethylbisphenol F type manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.) Epoxy resin), Ephotote YDC-1312 (hydroquinone type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), Ephotote YDPN-638, Ephotote YDPN -63X (Phenol novolac-type epoxy resin manufactured by Shinnittetsu Sumikin Co., Ltd.), Ephotote YDCN-701 (cresol novolac-type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), Ephotote ZX-1201 (Shinnittetsu Sumikin) Bisphenol fluorene type epoxy resin manufactured by Chemical Co., Ltd.), TX-0710 (Bisphenol S type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), Epicron EXA-1515 (bisphenol S type epoxy resin manufactured by Dai Nippon Chemical Industries, Ltd.), NC- 3000 (Biphenylaralkylphenol-type epoxy resin manufactured by Nippon Explosives Co., Ltd.), Ephotote ZX-1355, Ephotote ZX-1711 (Naphthalenediol type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), Ephotote ESN-155 (Shinnittetsu Sumikin Chemical Co., Ltd. β-naphthol aralkyl type epoxy resin), Ephotote ESN-355, Epotho ESN-375 (Shinnittetsu Sumikin Chemical Co., Ltd. dinaphthol aralkyl type epoxy resin), Ephoto ESN-475V, Ephotote ESN-485 (α-naphthol aralkyl type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), EPPN-501H (trisphenylmethane type epoxy resin manufactured by Nippon Explosives Corporation), Sumiepoxy TMH-574 (Trisphenylmethane type epoxy water manufactured by Sumitomo Chemical Co., Ltd.) G), YSLV-120TE (bisthioether-type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), Ephotote ZX-1684 (resorcinol-type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), Epicron HP-7200H (DIC Dicyclopentadiene type epoxy resin manufactured by Co., Ltd.), TX-0929, TX-0934, TX-1032 (alkylene glycol type epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), Celoxide 2021 (aliphatic ring manufactured by Daicel Chemical Industries, Ltd.) Type epoxy resin), Epotot YH-434 (Diaminodiphenylmethane tetraglycidylamine manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), jER 630 (Aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation), Ephotote FX- 289B, Ephotot FX-305, TX-0932A (phosphorus-containing epoxy resin manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.), urethane-modified epoxy resins, and oxazolidone ring-containing epoxy resins, etc., but are not limited thereto. . In addition, these epoxy resins may be used alone or in combination of two or more.

Although the epoxy resin composition of the present invention essentially contains the phenol compound (B) represented by the general formula (1) as a curing agent component, other epoxy resin curing agents may be used in combination within the range not impairing the object of the present invention.

Specific examples of other epoxy resin curing agents that can be used in combination include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol S, bisphenol Z, bisphenol fluorene, tetramethylbisphenol A, tetramethylbisphenol F. , Tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenylsulfide, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-biphenol, 3,3 ',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert -Divalent phenols such as butylhydroquinone, di-tert-butylhydroquinone, dihydroxynaphthalene, and dihydroxymethylnaphthalene, trihydroxynaphthalene, tris-(4-hydroxyphenyl)methane, 1,1, Trivalent or higher phenols such as 2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, and o-cresol novolac, co-condensed phenols obtained from dicyclopentadiene and phenols, cresols and formaldehyde, and Cocondensed phenols obtained from alkoxy group-substituted naphthalenes, phenolaralkyl-based phenols obtained from phenols and paraxylylenedichloride, phenols, biphenylaralkyl-based phenols obtained from bischloromethylbiphenyl, etc., naphthols, and And naphthol aralkyl-based phenols synthesized from paraxylylene dichloride and the like.

Other epoxy resin curing agents include acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid, diethylenetriamine, and triethylenetetramine. , Metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, dicyandiamide, dimer acid, etc. Compounds, phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4methylimidazole, 2- Imidazoles such as undecylimidazole and 1-cyanoethyl-2-methylimidazole, and imidazole salts, which are salts of trimellitic acid, isocyanuric acid, boron, etc., benzyldimethylamine, 2,4 Amines such as ,6-tris(dimethylaminomethyl)phenol, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds and salts of them and phenols, phenol novolac resins, etc. Complex compounds, aromatic phosphonium or iodonium salts, and the like.

These epoxy resin curing agents may be used alone or in combination of two or more. These blending amounts may be within a range that does not impair the object of the present invention, but with respect to the total of the phenolic compound (B) represented by the general formula (1) and the other epoxy resin curing agent, it is preferably less than 50% by mass, more preferably It is less than 40 mass%, More preferably, it is less than 25 mass%.

In addition, in the epoxy resin composition of the present invention, the compounding amount of the epoxy resin curing agent is 0.4 to 1.2 moles of the active hydrogen group of the epoxy resin curing agent containing the phenol compound (B) with respect to 1 mole of the epoxy group of the epoxy resin (A). The range is preferable, 0.5 to 1.1 moles are more preferable, and 0.7 to 1.0 moles are still more preferable. Even if there are few or more epoxy resin curing agents for the epoxy group, there is a fear that the curing is incomplete and good curing properties may not be obtained. In addition, the active hydrogen group of an epoxy resin curing agent represents a functional group reacting with an epoxy group, and specifically, a phenolic hydroxyl group, an amino group, a carboxyl group, etc. are mentioned.

In the epoxy resin composition of the present invention, a curing accelerator may be used as needed. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, Tertiary amines such as 1,8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, Metal compounds, such as tin octylate, are mentioned. The curing accelerator may be used alone or in combination of two or more. The curing accelerator is used in an amount of 0.02 to 5.0 parts by mass based on 100 parts by mass of the epoxy resin (A) in the epoxy resin composition of the present invention. By selectively using these curing accelerators, the curing temperature can be lowered or the curing time can be shortened.

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

The epoxy resin composition of the present invention may contain a curable resin other than the epoxy resin or a thermoplastic resin within a range that does not impair the properties. Specifically, phenol resin, acrylic resin, petroleum resin, indene resin, indencumaron resin, phenoxy resin, cyanate resin, epoxy acrylate resin, vinyl compound, polyurethane, polyester, polyamide, polyimide, Polyamideimide, polyetherimide, bismaleimide triazine resin, polyethersulfone, polysulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl formal, and the like, but are not limited thereto.

In the epoxy resin composition of the present invention, a filler may be used as needed. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium hydroxide, glass powder, and silica balloon. You can do it. An improvement in impact resistance is mentioned as a reason for using a general inorganic filler. Further, fibrous fillers such as glass fibers, pulp fibers, synthetic fibers, and ceramic fibers, and organic fillers such as particulate rubber and thermoplastic elastomer may be blended.

Further, in the epoxy resin composition of the present invention, if necessary, additives such as a flame retardant, a thixotropic agent, and a fluidity improver may be blended. Examples of the thixotropic imparting material include silicone-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite-based. In addition, if necessary, the resin composition of the present invention contains a release agent such as carnava wax and OP wax, a colorant such as carbon black, a flame retardant such as antimony trioxide, a low stress agent such as silicone oil, and a lubricant such as calcium stearate. can do.

Next, the prepreg obtained by using the epoxy resin composition of the present invention will be described. As the sheet-like substrate, a woven or nonwoven fabric made of inorganic fibers such as glass and organic fibers such as polyester, polyamine, polyacrylic, polyimide, and Kevlar may be used, but is not limited thereto. The method of producing a prepreg from the epoxy resin composition and substrate of the present invention is not particularly limited, for example, after immersing the substrate in a resin varnish obtained by adjusting the viscosity of the epoxy resin composition with a solvent and impregnating it, It is heat-dried, and is obtained by semi-curing (B-stage) a resin component, and can be, for example, heat-dried 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 by using the epoxy resin composition of the present invention will be described. Although it does not specifically limit as a method of manufacturing an adhesive sheet, For example, the epoxy resin composition of this invention is preferably 5 to 5 on a carrier film which does not dissolve in an epoxy resin composition such as a polyester film or a polyimide film. After coating to a thickness of 100 µm, it is heated and dried at 100 to 200°C for 1 to 40 minutes to form a sheet. In general, a resin sheet is formed by a method called a casting method. At this time, if the sheet to which the epoxy resin composition is applied is previously subjected to surface treatment with a release agent, the molded adhesive sheet can be easily peeled off. Here, the thickness of the adhesive sheet is preferably 5 to 80 µm. The adhesive sheet thus obtained is usually an insulating adhesive sheet having insulation, but a conductive adhesive sheet can be obtained by mixing a conductive metal or metal-coated fine particles with an epoxy resin composition.

Next, a method of manufacturing a laminated plate using the prepreg or the insulating adhesive sheet of the present invention will be described. In the case of forming a laminate using a prepreg, one or a plurality of prepregs are laminated, and metal foils are disposed on one or both sides to form a laminate, and the laminate is heated and pressed to form a laminated body. Here, as the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, true oil, and nickel can be used. Conditions for heating and pressurizing the laminate may be appropriately adjusted under the conditions under which the epoxy resin composition is cured and heated and pressurized. However, if the pressure of the pressurization is too low, bubbles may remain inside the resulting laminate and the electrical properties may be degraded. Therefore, it is preferable to pressurize under conditions that satisfy moldability. For example, the temperature can be set to 160 to 220°C, the pressure to 49.0 to 490.3 N/cm 2 (5 to 50 kgf/cm 2 ), and the heating time to 40 to 240 minutes, respectively. Further, a multilayered plate can be manufactured using the single-layered laminate thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminate by an additive method or a subtractive method, and the formed circuit surface is treated with an acid solution to perform blackening treatment to obtain an inner layer material. An insulating layer is formed with a prepreg or an insulating adhesive sheet on one or both sides of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multilayer plate. In the case of forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is disposed on the circuit formation surface of a plurality of inner layer materials 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, by heat-pressing and integrally forming this laminate, the cured product of the insulating adhesive sheet is formed as an insulating layer, and a multilayered inner layer material is formed. Alternatively, a cured product of an insulating adhesive sheet is formed as an insulating layer by using an inner layer material and a metal foil as a conductor layer. Here, as the metal foil, the same one used for the laminated plate used as the inner layer material can be used. Moreover, heat-press molding can be performed under the same conditions as the molding of the inner layer material. In the case of forming the insulating layer by applying the epoxy resin composition to the laminate, the circuit forming surface resin of the outermost layer of the inner layer material is applied to a thickness of preferably 5 to 100 μm, and then 100 to 200°C. It is formed into a sheet by heating and drying for 1 to 90 minutes. It is generally formed by a method called a casting method. The thickness after drying is preferably 5 to 80 µm. A printed wiring board can be formed by further forming via holes or circuit formation on the surface of the multilayered laminate thus formed by the additive method or the subtractive method. Further, by repeating the above construction method using this printed wiring board as an inner layer material, a multilayered laminate can be further formed. In the case of forming an insulating layer with a prepreg, a stack of one or more prepregs is disposed on the circuit formation surface of the inner layer material, and a metal foil is disposed on the outer side thereof to form a laminate. Then, by heat-pressing and integrally forming this laminate, the cured product of the prepreg is formed as an insulating layer, and the metal foil on the outside thereof is formed as a conductor layer. Here, as the metal foil, the same thing as the one used for the laminated plate used as the inner layer plate can also be used. Moreover, heat-press molding can be performed under the same conditions as the molding of the inner layer material. A printed wiring board can be formed by further forming via holes or circuit formation on the surface of the multilayer laminate thus formed by the additive method or the subtractive method. Further, by repeating the above construction method using this printed wiring board as an inner layer material, it is possible to further form a multilayered multilayer board.

Further, when the epoxy resin composition of the present invention is cured by heating, it can be set as an epoxy resin cured product, and this cured product becomes excellent in terms of low dielectric properties, heat resistance, and low hygroscopicity. This cured product can be obtained by molding an epoxy resin composition by a method such as molding, compression forming, transfer forming, 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, adhesive sheet, laminate, sealant, mold, and cured product obtained by using the composition exhibited excellent low dielectric properties, heat resistance, low moisture absorption, and excellent adhesion properties.

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 Examples, unless otherwise specified, parts represent "parts by mass", and% represents "% by mass".

(1) Epoxy equivalent measurement

It measured according to JIS K 7236 standard. Specifically, a potentiometric titrator was used, methyl ethyl ketone was used as a solvent, a tetraethylammonium bromide solution was added, and a 0.1 mol/L perchloric acid-acetic acid solution was used.

(2) Measurement of phosphorus content

Sulfuric acid, hydrochloric acid, and perchloric acid were added to the sample, followed by heating to wet incineration, and all phosphorus atoms were made into orthophosphoric acid. Metavanadate and molybdate were reacted in an acidic solution of sulfuric acid, and the absorbance at 420 nm of the resulting invanadomolybdic acid complex was measured, and the phosphorus atom content was expressed in %. In addition, B stage resin powder was used for the measurement sample of the epoxy resin composition.

(3) Measurement of phenolic hydroxyl group equivalent

THF containing 4% methanol was added to the sample, 10% tetrabutylammonium hydroxide was added, and the absorbance between 400 nm and 250 nm was measured using an ultraviolet visible spectrophotometer to give a phenolic hydroxyl group to a hydroxyl group. It was calculated as the number of grams of sample per equivalent.

(4) Measurement of water absorption

In accordance with JIS C 6481, measurement was performed by weight change before and after immersion at 23°C for 24 hours.

(5) Measurement of relative permittivity and dielectric loss tangent

A value of 1 GHz was measured by a cavity resonance method (Vector Network Analyzer (VNA) E8363B (manufactured by Agilent Technologies), a cavity resonator perturbation method permittivity measuring device (manufactured by Kanto Electronics Co., Ltd.)).

(6) Measurement of adhesion

In conformity with JIS K 6854-1, it measured by 50 mm/min in 25 degreeC atmosphere by the Shimadzu Corporation autograph.

(7) Measurement of water resistance

Solder heat resistance after PCT was measured as an index of water resistance. The test piece prepared according to 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, and those that did not cause swelling or peeling for 20 minutes or more were set to ○, and within 10 minutes. The occurrence of swelling or peeling was designated as x, and other values were evaluated as △.

(8) T-288 test

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

(9) Measurement of glass transition temperature

It was measured in accordance with JIS K 7121 and differential scanning calorimetry. It measured by the temperature rising rate of 10 degreeC/min at 20 degreeC using the EXTER DSC6200 manufactured by SII, and calculated|required from the extrapolation glass transition start temperature (Tig) of the DSC chart obtained in the 2nd cycle.

(10) Measurement of flame retardancy

After removing the copper foil from the copper clad laminate by immersing it in an etching solution, washing and drying, a test piece cut into length 127 mm and width 12.7 mm was used, and the test method of UL94 (Safety Certification Standard of Underwriters Laboratories Inc.) was used. It was ignited according to (V method) and the combustion time was measured. Evaluation was described as V-0, V-1, and V-2. However, what burned completely was described as "combustion".

Synthesis Example 1 (Synthesis of phenol compound (B1))

Into a four-neck glass separable 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 injected and stirred, and bis( 550 parts of 4-hydroxy-3,5-dimethylphenyl)sulfone (hereinafter, TMBPS) was added to obtain 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, and 75 while stirring. It heated up to degreeC and reacted for 2 hours.

After the reaction was completed, the resulting salt was removed by filtration, the temperature was raised to 100°C under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 1290 parts of toluene was added to dissolve. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 526 parts of a pale yellow solid phenol compound (B1). The phenolic hydroxyl group equivalent of the obtained phenol compound was 156 g/eq.

Synthesis Example 2 (Synthesis of phenol compound (B2))

Into a four-neck glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, 367 parts of methanol and 91.7 parts of potassium hydroxide were injected and stirred, and TMBPS was used as the dihydroxy compound (a). 250 parts was added to obtain an alkali metal salt. Thereafter, 61.5 parts of BCMB as a halogenated methyl group-containing compound (b) and 360 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 the reaction was completed, the formed salt was removed by filtration, the temperature was raised to 100° C. under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 685 parts of toluene was added to dissolve. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 279 parts of a pale yellow solid phenol compound (B2). The phenolic hydroxyl group equivalent of the obtained phenol compound was 250 g/eq.

Synthesis Example 3 (Synthesis of phenol compound (B3))

Into a four-neck glass separable 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 injected and stirred, and TMBPS was used as the dihydroxy compound (a). 220 parts were added to obtain an alkali metal salt. Thereafter, 90.2 parts of BCMB as a halogenated methyl group-containing compound (b) and 401 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 the reaction was completed, the resulting salt was removed by filtration, the temperature was raised to 100°C under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 663 parts of toluene was added to dissolve. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 261 parts of a pale yellow solid phenol compound (B3). The phenolic hydroxyl group equivalent of the obtained phenol compound was 432 g/eq.

Synthesis Example 4 (Synthesis of phenol compound (B4))

Into a four-neck glass separable 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 stirred, and TMBPS was used as the dihydroxy compound (a). 200 parts was added to obtain an alkali metal salt. Thereafter, 114.8 parts of BCMB as a methyl halide group-containing compound (b) 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 the reaction was completed, the resulting salt was removed by filtration, the temperature was raised to 100°C under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 657 parts of toluene was added to dissolve. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 253 parts of a pale yellow solid phenol compound (B4). The phenolic hydroxyl group equivalent of the obtained phenol compound was 702 g/eq.

Synthesis Example 5 (Synthesis of phenol compound (B5))

Into a four-neck glass separable 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 stirred, and TMBPS was used as the dihydroxy compound (a). 200 parts was added to obtain an alkali metal salt. Thereafter, 123 parts of BCMB as a halogenated methyl group-containing compound (b) 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 the reaction was completed, the resulting salt was removed by filtration, the temperature was raised to 100° C. under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 670 parts of toluene was poured for dissolution. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 230 parts of a pale yellow solid phenol compound (B5). The phenolic hydroxyl group equivalent of the obtained phenol compound was 1018 g/eq.

Synthesis Example 6 (Synthesis of phenol compound (B6))

Into a four-neck glass separable 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 stirred, and TMBPS was used as the dihydroxy compound (a). 200 parts was added to obtain an alkali metal salt. Thereafter, 57.2 parts of bischloromethylbenzene (P-xylylenedichloride: PXDC) as a halogenated methyl group-containing compound (b) and 307 parts of bis(2-methoxyethyl) ether as a solvent were added, followed by stirring at 75°C. The temperature was raised to and reacted for 2 hours.

After the reaction was completed, the resulting salt was removed by filtration, the temperature was raised to 100° C. under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 544 parts of toluene were poured for dissolution. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 215 parts of a pale yellow solid phenol compound (B6). The phenolic hydroxyl group equivalent of the obtained phenol compound was 399 g/eq.

Synthesis Example 7 (Synthesis of phenol compound (B7))

Into a four-neck glass separable 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 injected and stirred, and tetramethyl as a dihydroxy compound (a). 250 parts of bisphenol F (hereinafter, TMBPF) was added to obtain 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, the temperature was raised to 75° C. while stirring, and reacted for 2 hours.

After the reaction was completed, the resulting salt was removed by filtration, the temperature was raised to 100°C under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 653 parts of toluene was added to dissolve. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 266 parts of a pale yellow solid phenol compound (B7). The phenolic hydroxyl group equivalent of the obtained phenol compound was 213 g/eq.

Synthesis Example 8 (Synthesis of phenol compound (B8))

Into a four-neck glass separable flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen gas introduction device, 257 parts of methanol and 64.1 parts of potassium hydroxide were injected and stirred, and bisphenol flue as a dihydroxy compound (a). 200 parts of oranges (hereinafter, BPFL) were added to obtain an alkali metal salt. Thereafter, 71.7 parts of BCMB as a halogenated methyl group-containing compound (b) 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 formed salt was removed by filtration, the temperature was raised to 100°C under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 585 parts of toluene was added to dissolve. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 203 parts of a pale yellow solid phenol compound (B8). The phenolic hydroxyl group equivalent of the obtained phenol compound was 484 g/eq.

Synthesis Example 9 (Synthesis of phenol compound (B9))

Into a four-neck glass separable 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 injected and stirred, and TMBPF was added to this as a dihydroxy compound (a). 125 parts was added to obtain an alkali metal salt. Thereafter, 55 parts of 1,5-bischloromethylnaphthalene (hereinafter referred to as BCMN) as a halogenated methyl group-containing compound (b) and 201 parts of bis(2-methoxyethyl) ether as a solvent were added, and the temperature was raised to 75°C while stirring. And reacted for 2 hours.

After the reaction was completed, the resulting salt was removed by filtration, the temperature was raised to 100°C under a reduced pressure of 50 mmHg, and the total amount of methanol and bis(2-methoxyethyl) ether was distilled off, and then 393 parts of toluene was added to dissolve. I did. After neutralizing and separating with phosphoric acid, washing and separating with water were repeated twice, and then toluene was distilled off to obtain 142 parts of a pale yellow solid phenol compound (B9). The phenolic hydroxyl group equivalent of the obtained phenol compound was 370 g/eq.

Synthesis Example 10 (Synthesis of epoxy resin (A3))

To a four-neck glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, YDPN-638 (manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., phenol novolac type epoxy resin, epoxy equivalent = 177 g/eq) 359 parts and 141 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA: manufactured by Sanko Corporation) were reacted at 160° C. for 4 hours to obtain a phosphorus-containing epoxy resin (A2). Got it. The epoxy equivalent of the obtained epoxy resin was 370 g/eq, and phosphorus content rate = 4.0%.

Synthesis Example 11 (Synthesis of epoxy resin (A6))

67 parts of HCA, 48 parts of 1,4-naphthoquinone, and 142 parts of toluene were put in a four-neck glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and 30 at 75°C. After stirring for a minute, after dehydration reaction at 110° C. for 90 minutes, 518 parts of ESN-485 (manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., naphthol aralkyl type epoxy resin, epoxy equivalent = 296 g/eq) was added, followed by heating toluene Was removed. Then, 0.01 part of triphenylphosphine (TPP) was added as a catalyst, and it was made to react at 160 degreeC for 4 hours, and obtained the phosphorus-containing epoxy resin (A5). The equivalent of the obtained epoxy resin was 551 g/eq and phosphorus content = 1.5%.

Synthesis Example 12 (Synthesis of epoxy resin (A7))

70 parts of HCA, 25 parts of 1,4-naphthoquinone, and 148 parts of toluene were put in a four-neck glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and 30 at 75°C. After stirring for minutes, after dehydrating at 110° C. for 90 minutes, 540 parts of NC-7700 (made by Nippon Explosives Co., Ltd., β naphthol cresol condensation type epoxy resin, epoxy equivalent = 222 g/eq) was added, followed by heating to remove toluene. Was carried out. Then, 0.01 part of TPP was added as a catalyst, and it was made to react at 160 degreeC for 4 hours, and obtained the phosphorus-containing epoxy resin (A6). The equivalent of the obtained epoxy resin was 372 g/eq and phosphorus content = 1.5%.

The epoxy resin, curing agent, and curing accelerator used in Examples and Comparative Examples are as follows.

Epoxy resin (A)

(A1): YDPN-638 (manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., phenol novolac epoxy resin, epoxy equivalent = 177 g/eq)

(A2): ESN-485 (manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., naphthol aralkyl type epoxy resin, epoxy equivalent = 296 g/eq)

(A3): Epoxy resin of Synthesis Example 10

(A4): TX-0821 (manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., phosphorus-containing epoxy resin, epoxy equivalent = 536 g/eq, phosphorus content = 3.0%)

(A5): TX-1106B (manufactured by Shinnittetsu Sumikin 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 12

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): Shounol BRG-557 (Showa Electric Co., Ltd. make, phenol novolac resin, phenolic hydroxyl group equivalent = 105 g/eq, softening point = 86°C)

(B11): TH-2500 (manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., bisphenol A type phenolic resin, phenolic hydroxyl group equivalent = 240 g/eq, softening point = 82°C)

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

Hardening accelerator

(C1): Qazole 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd., 2-ethyl-4-methylimidazole)

Examples 1 to 12 and Comparative Examples 1 to 2

While heating the curing agent (B) at 120 degreeC to the epoxy resin (A) heated by the compounding prescription shown in Table 1, it stirred and made it uniform, and the epoxy resin composition was obtained. The resulting epoxy resin composition was degassed under reduced pressure at the same temperature, and then a curing accelerator was added to carefully homogenize the air bubbles so as not to be swept into a mold and molded into a mold. Cured to obtain a cured product. Table 1 shows the evaluation results of the obtained molded cured product.

Examples 13 to 18 and Comparative Examples 3 to 8

An epoxy resin (A), a curing agent (B), a curing accelerator, and a solvent were blended according to the formulation shown in Table 2 to obtain an epoxy resin composition varnish having a nonvolatile content of 50%. The epoxy resin (A), the curing agent (B), and the curing accelerator were previously dissolved in methyl ethyl ketone (MEK) and used. After impregnating the obtained epoxy resin composition varnish into a glass cloth (manufactured by Nittobo Corporation, IPC standard 2116), the impregnated cloth was dried in a hot air circulation oven at 150°C for 7 minutes to obtain a B-stage prepreg. One of the obtained prepregs was stacked with four prepregs and copper foil (manufactured by Mitsui Metal Mining Co., Ltd., 3EC-III, thickness 35 µm) for lamination molding, and a temperature condition of 130°C x 15 minutes + 190°C x 80 minutes Then, a 2 MPa vacuum press was performed to obtain a 0.5 mm-thick laminate. The other is to use about 10 g of B-stage resin powder obtained from pulverization of the prepreg sheet for the purpose of molding a cured resin alone for measuring dielectric properties, and under the same vacuum press curing conditions using a Teflon frame type. A resin plate having a thickness of 2 mm was obtained. Table 2 shows the evaluation results of these obtained moldings.

Since the epoxy resin composition of the present invention has lower dielectric properties and better heat resistance than the conventional epoxy resin composition, electrical insulation is required and electrical high reliability is required for electronic circuit boards or sealants, especially for fine wiring electronic circuits. It is useful in substrate applications.

Claims (8)

As an epoxy resin composition containing an epoxy resin (A) and a phenol compound (B) represented by the following general formula (1), the epoxy resin (A) is a novolac-type epoxy resin (A) or 0.5 to 6.0 mass% An epoxy resin composition characterized by being an epoxy resin (A) containing 50 to 100% by mass of a phosphorus-containing epoxy resin having a phosphorus content.

(In the formula, m is a repeating number, and the average value is 0 <m <10. X and Y are a phenylene group, a naphthylene group, or a general formula (2) which may have a hydrocarbon group having 1 to 10 carbon atoms as a substituent or a halogen atom. It is at least 1 type of group selected from the group represented by ), and 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 as or different from each other. R ₂ is a single bond or a divalent group.) The method of claim 1,
The phenolic compound (B) is in the range of 0.001 to 1.0 mol of the halogenated methyl group-containing compound (b) represented by the following general formula (4) with respect to 1 mol of the dihydroxy compound (a) represented by the following general formula (3). Epoxy resin composition which is a phenol compound (B) obtained by reacting in.

(In the formula, Y is at least one group selected from a hydrocarbon group having 1 to 10 carbon atoms or a phenylene group, a naphthylene group, or a group represented by the general formula (2) which may have a halogen atom as a substituent.)

(In the formula, X is at least one group selected from a hydrocarbon group having 1 to 10 carbon atoms as a substituent or a phenylene group, a naphthylene group, or a group represented by the general formula (2) which may have a halogen atom. Z is a halogen Represents an 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 as or different from each other. R ₂ is a single bond or a divalent group.) The method of claim 1,
The epoxy resin composition in which the active hydrogen group of the epoxy resin curing agent containing the phenol compound (B) is in the range of 0.4 to 1.2 moles per 1 mole of the epoxy group of the epoxy resin (A). A prepreg characterized by using the epoxy resin composition according to any one of claims 1 to 3. An adhesive sheet characterized by using the epoxy resin composition according to any one of claims 1 to 3. Epoxy resin laminated board characterized by using the epoxy resin composition in any one of Claims 1-3. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 3. delete