KR20170131267A - Epoxy resin composition and cured product thereof - Google Patents

Abstract

Provided are an epoxy resin composition which has excellent performance in heat resistance, dielectric properties, adhesion properties and the like, and is useful in uses of lamination, forming, mold, adhesion and the like, and a cured product of the epoxy resin composition. The epoxy resin composition of the present invention contains an epoxy resin (A) and a curing agent (B), the epoxy resin (A) containing an epoxy resin (c) represented by chemical formula (1) and an oxazolidone ring-containing epoxy resin (a) obtained from an isocyanate compound (d), and the curing agent (B) containing a bisphenol compound (b1) represented by chemical formula (2) and a novolac phenol compound (b2) represented by chemical formula (3). X^1 and X^2 are a cycloalkylidene group with 5 to 8 ring atoms which has a hydrocarbon group as a substituent, A^1 is a benzene ring, a naphthalene ring, or a biphenyl ring, and T is a cross-linking group of a methylene group and the like.

Description

EPOXY RESIN COMPOSITION AND CURED PRODUCT THEREOF [0002]

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

Advances in electrical and electronic devices are remarkable, and in particular, in order to carry out high-speed and high-speed processing of data, communication apparatuses are required to have low dielectric constant and low dielectric tangent of electronic equipment members such as printed wiring boards and sealing materials Demand is getting stronger. In addition, although the wiring by the metal foil secures the adhesive force by roughening the bonding surfaces, it is necessary to suppress the harmonization for high-speed processing, and the problem of maintenance of the adhesive force has also become a problem.

BACKGROUND ART Infrastructure devices such as a portable device, which is one of uses of a printed wiring board, and a base station connecting thereto, have been always required to have high functionality along with the recent increase in the amount of dramatic information. In a portable device, a multi-layered or micro-wiring is progressing for the purpose of miniaturization, a material having a lower dielectric constant is required in order to thin a substrate, and a bonding surface is reduced by fine wiring, Is required. In order to suppress attenuation of a signal due to a high frequency in a substrate for a base station, a material having a lower dielectric tangent is required.

Properties such as low dielectric constant, low dielectric tangent, and high adhesive strength are largely derived from the structures of epoxy resin and curing agent, which are matrix resins of printed wiring boards.

It is known that the hydroxyl groups generated when the epoxy resin composition is cured deteriorate the dielectric constant. Patent Document 1 discloses an oxazolidone ring-containing epoxy resin in which an oxazolidone ring is formed by the reaction of an epoxy resin with an isocyanate as one of the inventions in which hydroxyl groups are reduced. Examples of the raw material epoxy resin include a compound obtained by glycidylating a divalent phenol such as bisphenol A, a compound obtained by glycidylating a tris (glycidyloxyphenyl) alkane, an aminophenol or the like, or a novolak type such as phenol novolac Are glycidylated. However, the disclosed epoxy resin does not sufficiently satisfy the requirements of the dielectric properties based on recent high-performance and has insufficient adhesiveness.

As a method for improving the dielectric property of the epoxy resin, as shown by the Clausius-Mossotti equation, it is effective to decrease the molar polarization rate and increase the molar volume. Patent Document 2 discloses a dicyclopentadiene-phenolic resin as a curing agent which utilizes the effect of increasing the molar volume. Patent Document 3 discloses a cycloalkylidene bisphenol containing a substituent such as 4,4 '- (3,3,5-trimethylcyclohexylidene) bisphenol, but there is no disclosure concerning dielectric properties.

On the other hand, Patent Documents 4 and 5 disclose an aromatic-modified phenol novolac as a curing agent. However, there is a problem that heat resistance and dielectric properties are excellent, but adhesive strength tends to be insufficient.

Japanese Unexamined Patent Publication No. 5-43655 Japanese Patent Publication No. 2015-535865 Japanese Patent Application Laid-Open No. 2-229181 Japanese Laid-Open Patent Publication No. 2010-235819 Japanese Laid-Open Patent Publication No. 2012-57079

Accordingly, an object to be solved by the present invention is to provide an epoxy resin composition and a cured product thereof, which are excellent in properties of low dielectric constant, high heat resistance and high adhesiveness and are useful for applications such as lamination, molding, casting, and bonding. It is another object of the present invention to provide an epoxy resin composition having excellent flame retardancy without deteriorating properties such as dielectric properties, heat resistance and adhesiveness even when a flame retardant is blended, and a cured product thereof.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies on low dielectric constant and low dielectric tangent materials. As a result, they have found that an epoxy resin containing an oxazolidone ring obtained by reacting an epoxy resin having a specific structure with an isocyanate compound, An epoxy resin composition comprising a combination of a curing agent combined with a specific novolak phenol compound achieves both a low dielectric constant and a low dielectric tangent which are not conventionally available, and a high glass transition temperature, and further has good adhesive force. Further, it has been found that even when used in combination with a flame retardant, excellent flame retardancy is exhibited without deteriorating properties such as dielectric properties, heat resistance, and adhesiveness.

That is, the present invention relates to an epoxy resin composition containing an epoxy resin (A) and a curing agent (B), wherein the epoxy resin (A) is an epoxy resin composition comprising an epoxy resin (c) represented by the following formula (1) and an isocyanate compound (B1) represented by the following formula (2) and a novolac phenol compound (b2) represented by the following formula (3), wherein the curing agent (B) contains an oxazoline ring- Wherein the epoxy resin composition is an epoxy resin composition.

[Chemical Formula 1]

In the formula, X ¹ represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one hydrocarbon group of 1 to 20 carbon atoms as a substituent. Each R ¹ independently represents a hydrogen atom, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom. And G represents a glycidyl group. n represents the number of repeats, and the average value is 0 to 5.

(2)

In the formula, X ² represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one hydrocarbon group of 1 to 20 carbon atoms as a substituent. R ² each independently represents a hydrogen atom, a halogen atom, a halogenated hydrocarbon group of 1 to 20 carbon atoms, or a hydrocarbon group of 1 to 20 carbon atoms which may have a heteroatom.

(3)

In the formulas, A ¹ each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups may have a hydrocarbon group having 1 to 49 carbon atoms which may have a hetero atom as a substituent , An aryl group having 6 to 48 carbon atoms, an aryloxy group having 6 to 48 carbon atoms, an aralkyl group having 7 to 49 carbon atoms, and an aralkyloxy group having 7 to 49 carbon atoms. T represents a divalent aliphatic cyclic hydrocarbon group or a divalent bridging group represented by the following formula (3a) or (3b). k represents 1 or 2; m represents the number of repeats, and the average value is 1.5 or more.

[Chemical Formula 4]

In the formulas, R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. A ² represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups may have a hydrocarbon group of 1 to 20 carbon atoms which may have a hetero atom as a substituent.

In the epoxy resin composition, it is a preferred embodiment of the present invention that at least one of the following is satisfied.

1) the mass ratio of the bisphenol compound (b1) to the novolak phenol compound (b2) is in the range of 5/95 to 95/5,

2) the bisphenol compound (b1) is 4,4 '- (3,3,5-trimethylcyclohexylidene) bisphenol or 4,4' - (3,3,5,5-tetramethylcyclohexylidene) bisphenol In fact,

3) the novolak phenol compound (b2) is a phenol compound represented by the following formula (4), or

4) The active hydrogen group of the curing agent (B) is 0.2 to 1.5 moles per mole of the epoxy group of the epoxy resin (A).

[Chemical Formula 5]

In the formulas, each R ⁷ independently represents a hydrocarbon group having 1 to 6 carbon atoms, and R ⁸ is a substituent represented by the following formula (4a). The average value of p is 0.1 to 2.5, q is 0 to 2, p + q is an average value of 0.1 to 3, and m is the same as m in formula (3).

[Chemical Formula 6]

In the formulas, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

Further, the present invention is an epoxy resin cured product obtained by curing the above epoxy resin composition.

The epoxy resin composition of the present invention imparts a cured product having a high glass transition temperature while maintaining good adhesion. In addition, the cured product of the present invention has excellent dielectric properties and exhibits good characteristics in the use of electronic materials requiring low dielectric constant and low dielectric tangent.

Hereinafter, embodiments of the present invention will be described in detail.

The epoxy resin composition of the present invention contains an epoxy resin (A) and a curing agent (B). The epoxy resin (A) contains an oxazolidone ring-containing epoxy resin (a) as an essential component. The curing agent (B) contains a bisphenol compound (b1) and a novolak phenol compound (b2) as essential components.

The epoxy equivalent (g / eq.) Of the oxazolidone ring-containing epoxy resin (a) is preferably from 200 to 1000, more preferably from 220 to 700, still more preferably from 230 to 500, still more preferably from 250 to 400 Do. When the epoxy equivalent is low, the content of the oxazolidone ring is decreased, and the hydroxyl group concentration in the cured product is increased, which may increase the dielectric constant. When the epoxy equivalent is high, the content of the oxazolidone ring is increased more than necessary, and the adverse effects such as deterioration of the solvent solubility and increase of the resin viscosity may be greater than the effect of improving the dielectric properties. In addition, since the crosslinking density of the cured product is lowered, the elastic modulus at the temperature of the solder reflow may be lowered, which may cause problems in use.

The softening point of the oxazolidone ring-containing epoxy resin (a) is preferably from 50 to 150 ° C., more preferably from 60 to 135 ° C., even more preferably from 70 to 110 ° C., in the case of being used for a prepreg or a film material Do. If the softening point is low, the resin varnish may be impregnated with glass cloth, and thereafter, the viscosity may be low when heated and dried in an oven, so that the adhesion amount of the resin may be reduced. When the softening point is high, the resin viscosity becomes high, and the impregnation property of the prepreg deteriorates, the solubility of the solvent deteriorates, the diluting solvent does not volatilize when heated and dried, There is a possibility of a problem.

The epoxy resin (a) containing an oxazolidone ring can be obtained advantageously by a method for producing an epoxy resin containing an oxazolidone ring described later, but is usually obtained as an oxazolidone ring-containing epoxy resin containing by-products and the like. Here, it is understood that by-products and the like include meaning of unreacted materials. The oxazolidone ring-containing epoxy resin (a) may be a reaction product containing these by-products or the like.

The oxazolidone ring-containing epoxy resin (a) is obtained by the reaction of the epoxy resin (c) represented by the formula (1) and the isocyanate compound (d). In this reaction, an epoxy group and an isocyanate group react to form an oxazolidone ring. Typically, when all of the bifunctional epoxy resin and isocyanate compound are used, they have structural units represented by the following formulas.

_{^{-E 1 -O-CH 2 -Ox 1}} -Ic 1 -Ox 1 -CH 2 -O-

Here, E ¹ is a residue obtained by removing a glycidyl ether group from an epoxy resin, Ox ¹ is an oxazolidone ring, and Ic ¹ is a residue obtained by removing an isocyanate group from an isocyanate.

In the formula (1), R ¹ independently represents a hydrogen atom, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom.

In the present specification, the hydrocarbon group which may have a hetero atom may be a hydrocarbon group or a hetero atom-containing hydrocarbon group having a part of carbon constituting the hydrocarbon group as a hetero atom. The hetero atom-containing hydrocarbon group is a hydrocarbon chain in which some of the carbon atoms constituting the hydrocarbon ring or the hydrocarbon ring is a hetero atom. In the case of a hydrocarbon chain, the hydrocarbon atom may be in the middle or at the terminal. The hetero atom may be oxygen, nitrogen, sulfur, or the like, but an oxygen atom is preferable. An aryloxy group, or an aralkyloxy group when the hetero atom is an oxygen atom, it is at the terminal, and the hydrocarbon group is an alkyl group, an aryl group or an aralkyl group. The hetero atom may be contained in a substituent such as a hydroxyl group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The halogenated hydrocarbon group having 1 to 20 carbon atoms is preferably a halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms.

The hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom may be a linear, branched, or cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an alicyclic hydrocarbon group having 6 to 20 carbon atoms Preferably an aromatic hydrocarbon group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, a cycloalkyl group of 5 to 8 carbon atoms, a cycloalkoxy group of 5 to 8 carbon atoms, an aryl group of 6 to 14 carbon atoms, More preferably an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, or an aralkyloxy group having 7 to 15 carbon atoms. These may be part of the carbon as a heteroatom.

Examples of the alkyl or alkoxy group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, Propoxy group, n-butoxy group, tert-butoxy group, and hexyloxy group. Examples of the cycloalkyl group or cycloalkoxy group having 5 to 8 carbon atoms include a cyclohexyl group and a cyclohexyloxy group. Examples of the aryl group or the aryloxy group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, an o-xylyl group, a naphthyl group, an indanyl group, a phenoxy group and a naphthyloxy group. Aralkyl groups having 7 to 15 carbon atoms or ar Examples of the alkyloxy group include benzyl, phenethyl, 1-phenylethyl, naphthylmethyl, anthracenylmethyl, benzyloxyl, naphthylmethyloxyl, They may be the same or different.

When flame retardancy is required, it is preferable to have a halogen atom or a halogenated hydrocarbon group having 1 to 20 carbon atoms as a substituent, and the halogen atom is preferably a bromine atom. Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a methyl bromide group and the like. However, in the later-described non-halogenated flame retardant epoxy resin composition, such a halogen atom-containing substituent is not included.

Preferred R ¹ is a hydrogen atom, a methyl group, a methoxy group, a phenyl group, a benzyl group, a 1-phenylethyl group, or a phenoxy group from the viewpoints of availability and cured product properties. The substitution position of R ¹ may be an ortho, para or meta position with respect to the carbon atom bonded to X ¹ , but is preferably an ortho or para position, and more preferably an ortho position.

In the formula (1), X ¹ is a cycloalkylidene group having 5 to 8 ring atoms and at least one hydrocarbon group having 1 to 20 carbon atoms as a substituent. The cycloalkane ring constituting the cycloalkylidene group is preferably a cyclopentane ring, a cyclohexane ring, a cycloheptane ring or a cyclooctane ring, and a cyclopentane ring or a cyclohexane ring is preferable.

The hydrocarbon group having 1 to 20 carbon atoms as a substituent is preferably a structure having a large molecular weight from the viewpoint of dielectric properties, and is preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, Aralkyl groups of 7 to 15 are preferred. Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group and a hexyl group. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, an o-xylyl group and a naphthyl group. Examples of the aralkyl group having 7 to 15 carbon atoms include a benzyl group , A phenethyl group, a 1-phenylethyl group, and the like. However, the present invention is not limited thereto. A preferable substituent is an alkyl group having 1 to 3 carbon atoms or a phenyl group, more preferably a methyl group, from the viewpoints of availability and physical properties of the cured product.

Also, the cycloalkylidene group is a 1,1-cycloalkylidene group, and the substituent may be a cycloalkylene group, a cycloalkylene group, a cycloalkylene group, a cycloalkylene group, a cycloalkylene group, It is believed that the mobility of the ring is limited to improve the dielectric properties and improve the heat resistance. This substitution position may be bonded at any position as far as it can restrict motility, but it is preferable that the substitution position is bonded to a carbon atom close to the 1-position of the cycloalkylidene group. The position of a preferable substituent is a carbon atom at the 2-position or 5-position in the cyclopentane ring. Position, 3-position, 5-position or 6-position carbon atom in the cyclohexane ring, and more preferably 2-position or 6-position carbon atom in the cyclohexane ring. In the cycloheptane ring, the carbon atom at the 2-position, the 3-position, the 6-position, or the 7-position is more preferable the carbon atom at the 2- or 7-position. In the cyclooctane ring, the carbon atom at the 2-position, the 3-position, the 4-position, the 6-position, the 7-position or the 8-position is more preferable the carbon atom at the 2-, 3- or 7- Is a carbon atom at the 2-position or the 8-position. However, depending on the influence of the steric hindrance with the adjacent benzene ring, it may be difficult to substitute with the carbon atom closest to the 1-position, and in that case, it is preferable that the substituent is bonded to the carbon atom next to the substituent. For example, in a cyclohexane ring, the carbon atom at the 2-position or 6-position is closest to the 1-position, but when substitution is difficult due to steric hindrance, the substituent may be bonded to the 3-position or 5-position next to the cyclo-hexane ring.

The number of substituents is required to be at least one for the reasons described above, but three or more is preferable, and three is more preferable from the viewpoint of physical properties such as heat resistance as a cured product.

In formula (1), n is a repetition number, and the average value (number average) is 0 to 5, preferably 0 to 3, more preferably 0 to 1, still more preferably 0 to 0.5, desirable. A single compound in which the repeating number is any one of 0 to 5, or a mixture in which n is a multiple of 0 to 5 may be used.

The epoxy equivalent of the epoxy resin (c) is preferably 100 to 500, more preferably 125 to 400, and even more preferably 150 to 300. The alcoholic hydroxyl group equivalent (g / eq.) Is preferably 3000 or more, more preferably 4000 or more, and still more preferably 5000 or more. It is not preferable that the alcoholic hydroxyl group has a small alcoholic hydroxyl equivalent since it reacts with isocyanate to form a urethane bond and lower the glass transition point of the cured product. In addition, since the concentration of hydroxyl groups in the cured product increases, it is also undesirable in terms of increasing the dielectric constant of the cured product.

Examples of the epoxy resin (c) include an epoxy resin obtained from a bisphenol compound containing a cycloalkylidene group represented by the formula (2) and epihalohydrin. For example, 4,4 '- (2-methylcyclohexylidene) diphenol glycidyl ether, 4,4' - (3-methylcyclohexylidene) diphenol glycidyl ether, 4,4 ' - (4-methylcyclohexylidene) diphenol glycidyl ether, 4,4 '- (3,3,5-trimethylcyclohexylidene) diphenol glycidyl ether, Trimethylcyclohexylidene) -bis-phenylphenol glycidyl ether, 4,4 '- (3,3,5-trimethylcyclohexylidene) -bis-dimethylphenol glycidyl ether, 4, 4'- (3,3,5-trimethylcyclohexylidene) -bis-tert-butylphenol glycidyl ether, but not limited thereto, and they may be used alone or in combination of two or more do.

As the epoxy resin (c), the following formula (5) is obtained from 4,4 '- (3,3,5-trimethylcyclohexylidene) bisphenol and epihalohydrin from the viewpoints of availability and cured product properties. Is preferably an epoxy resin (c1). Further, in the equation (5), n corresponds to n in the equation (1).

(7)

To prepare the oxazolidone ring-containing epoxy resin (a), a desired oxazolidone ring-containing epoxy resin can be obtained by the reaction of the epoxy resin (c) and the isocyanate compound (d). The isocyanate compound (d) can be an isocyanate compound having an average of at least 1.8 isocyanate groups (-N = C = O) in one molecule, that is, a polyfunctional isocyanate compound having a bifunctional or higher functionality, Can be used. The monofunctional isocyanate compound may be contained in a small amount but is effective for the purpose of lowering the degree of polymerization because it becomes a terminal group, but the degree of polymerization does not rise.

Specific examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,5-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethyl xylylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, (Methylene) diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, naphthalene-1,4-diylbis Isocyanate, p-phenylenediisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate, 2,3'-dimethoxybisphenyl- - diisocyanate, diphenylmethane-4,4'-diisocyanate Dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfate-4,4'- Diisocyanate, diphenylsulfone-4,4'-diisocyanate, bicyclo [2.2.1] heptane-2,5-diylbis methylene diisocyanate, bicyclo [2.2.1] heptane-2,6- Diisocyanate, isophorone diisocyanate, 4,4'-methylenebiscyclohexyldiisocyanate, lysine diisocyanate, 1,1-bis (isocyanatomethyl) cyclohexane, 1,2-bis (isocyanatomethyl) Cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, Cyclohexylene diisocyanate, 2-methyl-1,3-cyclohexylene diisocyanate, 1-methylbenzene-2,4-diisocyanate Methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl Diisocyanate, butane-1,1-diisocyanate, butane-1,1-diisocyanate, butane-1,1-diisocyanate, isobutylene diisocyanate, Butene-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane- , Pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, , Nonane-1, 9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilanediisocyanate (Isocyanato-phenyl) thio (meth) acrylate, and tricyclodecane isocyanate compounds such as triphenylmethane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, bicycloheptane triisocyanate, Polyfunctional isocyanate compounds such as phosphate, lysine ester triisocyanate, undecane triisocyanate, tris (4-phenylisocyanate thiophosphate) -3,3 ', 4,4'-diphenylmethane tetraisocyanate and polymethylene polyphenylisocyanate , Block-type isocyanates masked by blocking agents such as alcohols or phenols, bis-urethane compounds, etc., but are not limited thereto. These isocyanate compounds may be used alone or in combination of two or more.

Among these isocyanate compounds, a bifunctional isocyanate compound or a trifunctional isocyanate compound is preferable, and a bifunctional isocyanate compound is more preferable. If the number of functional groups of the isocyanate compound is large, there is a fear that the storage stability is lowered, and if it is small, heat resistance and dielectric properties may not be improved. More preferred isocyanate compounds are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,5-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'- Isocyanate, isocyanate, 4,4'-diphenylmethane diisocyanate, m-xylylenediisocyanate, p-xylylene diisocyanate, tetramethyl xylylene diisocyanate, 1,4-naphthalenediyl diisocyanate, Isocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, 3,3'-dimethylbisphenyl-4,4'-diisocyanate, m-phenylenediisocyanate, Hexane-1,4-diisocyanate, cyclohexane-1,3-diylbis methylene diisocyanate, cyclohexane-1,4-diylbis methylene diisocyanate, hexamethylene diisocyanate, 2,2,4 - trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4,4'-methylenebiscyclohexyldiisocyanate, bicyclo [2.2.1] heptane-2,5-diylbis methylene diisocyanate, Bicyclo [2.2.1] heptane-2,6-diylbis methylene diisocyanate, and isophorone diisocyanate. Particularly preferred isocyanate compounds (d) among these are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,5-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4 ' -Diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, cyclohexane-1,3-diylbis methylene diisocyanate, cyclohexane-1,4-diylbis methylene diisocyanate, and isophorone diisocyanate And at least one selected from the group consisting of

The reaction between the epoxy resin (c) and the isocyanate compound (d) can be carried out by a known method. Specific reaction methods include: (1) removing the moisture in the epoxy resin by melting the epoxy resin (c) and purging the dry gas or reducing the pressure in the system; adding the isocyanate compound (d) (2) a method in which the epoxy resin (c) and the catalyst are mixed in advance and the dry gas is purged or the pressure in the system is reduced to remove moisture in the epoxy resin, and then the isocyanate compound (d) is added And the reaction is carried out. The water content in the system at this time is preferably 0.5 mass% or less, more preferably 0.1 mass% or less, and still more preferably 0.05 mass% or less. In any of these methods, a non-reactive solvent may be used if necessary, for example, when the viscosity of the resin is high and stirring is difficult. In this way, the epoxy group of the epoxy resin (c) reacts with the isocyanate group of the isocyanate compound (d) to form an oxazolidone ring. When n in the formula (1) is 1 or more, an alcoholic hydroxyl group is included, and the isocyanate group of the alcoholic hydroxyl group and the isocyanate compound (d) undergoes addition reaction to form a urethane bond. Except for the case where n in the formula (1) is 0, impurities added in the urethane bond are present. The oxazolidone ring-containing epoxy resin (a) used in the present invention includes not only an oxazolidone ring-containing epoxy resin but also an unreacted starting epoxy resin (c). It may contain an impurity added in the urethane bond. These mixtures are also included in the epoxy resin (a) containing an oxazolidin ring used in the present invention.

The epoxy equivalent (No) of the epoxy resin (a) containing an oxazolidone ring can be predicted from the kind of the starting material and the amount of injection by the following calculation formula. Conversely, the desired epoxy equivalent of the epoxy resin (a) containing an oxazolidone ring is calculated from the epoxy equivalent (Ne) of the epoxy resin (c) and the equivalent (Ni) of the isocyanate group of the isocyanate compound , And the injection amount of the epoxy resin (c) and the isocyanate compound (d) can be obtained. Also, the equivalent unit is g / eq. , And so on unless otherwise stated.

Me: injection amount (g) of epoxy resin (c)

Mi: amount of injection (g) of isocyanate compound (d)

For example, when the epoxy equivalent of the epoxy resin (c) is 220 and the equivalent of the isocyanate group of the isocyanate compound (d) is 125, the amount of the epoxy equivalent of the epoxy resin (a) , And from the above calculation formula, the isocyanate compound (d) is 30 parts by mass based on 100 parts by mass of the epoxy resin (c).

The oxazolidone ring modification ratio of the oxazolidin ring-containing epoxy resin (a) used in the present invention is preferably from 0.15 to 10 parts by weight, from the viewpoints of suppressing high viscosity, securing solvent solubility, and improving toughness, 0.6, more preferably 0.2 to 0.5, still more preferably 0.25 to 0.45. If the oxazolidone ring modification ratio is large, it may become a large molecule to increase the viscosity or lower the solubility of the solvent. When the oxazolidone ring modification ratio is small, oxazolidone ring which is rigid and has high molecular interaction is small, and the effect of improving the heat resistance and adhesiveness of the cured product is insufficient, and there are many glasses of glass produced at the time of curing, The effect of improving the characteristics is also insufficient. Since the oxazolidone ring modification ratio is substantially determined by the ratio of the epoxy group and the isocyanate group to be used, the oxazolidone ring modification ratio is defined by the following formula in the present specification.

Oxazolidone ring modification ratio = (isocyanate group mol) / (epoxy group mole)

For example, in the case of the epoxy resin containing an oxazolidone ring having an epoxy equivalent of about 500, the oxazolidone ring modification ratio is 0.53.

Specific examples of the non-reactive solvent that can be used in the reaction of the epoxy resin (c) and the isocyanate compound (d) include hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene , Xylene and ethylbenzene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ketones such as ethyl ether, isopropyl ether, butyl ether, diisobutyl ether, methylphenyl ether, ethylphenyl Ethers such as ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methylfuran, tetrahydrofuran, diethylene glycol dimethyl ether, ethylene glycol diethyl ether and methyl ethylcarbitol, methyl cellosolve acetate, cellosolve acetate , Butyl cellosolve acetate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and diethyl oxalate, Amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide, lactones such as? -Butyrolactone, sulfoxides such as dimethylsulfoxide, And urea such as tetramethylurea and halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene and o-dichlorobenzene. However, the present invention is not limited to these The non-reactive solvent may be used alone or in combination of two or more. The amount of these solvents to be used is preferably 1 to 900 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the epoxy resin (c).

The reaction between the epoxy resin (c) and the isocyanate compound (d) is preferably carried out by adding a catalyst. The addition temperature of the catalyst is preferably in the range of room temperature to 150 ° C, more preferably in the range of room temperature to 100 ° C.

The reaction temperature is preferably 100 to 250 ° C, more preferably 100 to 200 ° C, and even more preferably 120 to 160 ° C. When the reaction temperature is low, formation of an oxazolidone ring is not sufficiently carried out, and an isocyanurate ring formed by a trimerization reaction of an isocyanate group is formed. In addition, when the reaction temperature is high, localized high molecular weight is produced and generation of an insoluble gel component is increased. Therefore, it is preferable to adjust the addition rate of the isocyanate compound (d) and maintain the reaction temperature at an appropriate temperature. By appropriately controlling the reaction conditions, it is possible to generate the oxazolidone ring approximately quantitatively from the epoxy group of the epoxy resin (c) and the isocyanate group of the isocyanate compound (d).

The reaction time is preferably in the range of 15 minutes to 10 hours from the end of the addition of the isocyanate compound (d), more preferably 30 minutes to 8 hours, further preferably 1 hour to 5 hours. If the reaction time is short, the isocyanate group may remain in the product in large amount, and if the reaction time is long, the productivity may be remarkably lowered.

The kind of the catalyst to be used in the reaction is not particularly limited as long as it is a basic catalyst. Specific examples thereof include lithium compounds such as lithium chloride and butoxy lithium, complex salts of boron trifluoride, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, Quaternary ammonium salts such as tetraethylammonium iodide and tetrabutylammonium iodide, dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine, N-methylmorpholine, N, N'-dimethylpiperazine , And 1,4-diethylpiperazine; phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine; amines such as amyltriphenylphosphonium bromide, diallyldiphenylphosphonium Bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, butyl Tetrabutylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, etc. Imidazoles such as 2-phenylimidazole, 2-methylimidazole and 2-ethyl-4-methylimidazole, and the like can be given. These catalysts may be used alone or in combination of two or more. Alternatively, it may be divided into several circuits and used.

Of these catalysts, quaternary ammonium salts, tertiary amines, phosphines or phosphonium salts are preferable, and tetramethylammonium iodide is more preferable in terms of reaction activity and selectivity of the reaction. With a catalyst having a low reaction activity, there is a fear that the reaction time is prolonged and the productivity is lowered. In the case of a catalyst having a low selectivity for the reaction, there is a possibility that polymerization reaction between the epoxy groups proceeds and objective properties can not be obtained.

The amount of the catalyst to be used is not particularly limited but is preferably 0.0001 to 5 mass%, more preferably 0.0005 to 1 mass%, more preferably 0.001 to 0.5 mass%, based on the total mass of the epoxy resin (c) and the isocyanate compound (d) , And more preferably 0.002 to 0.2 mass%. If the amount of the catalyst is large, the self-polymerization reaction of the epoxy group proceeds in some cases, so that the resin viscosity becomes high. Further, the self-polymerization reaction of the isocyanate is promoted, and the formation of the oxazolidone ring is suppressed. In addition, there is a risk of lowering the insulating property and decreasing the moisture resistance when remaining as impurities in the produced resin and used for various applications, particularly as a material for a laminate or an encapsulating material.

The curing agent (B) includes the bisphenol compound (b1) represented by the formula (2) and the novolac phenol compound (b2) represented by the formula (3). The mixing ratio (b1 / b2; mass ratio) of the bisphenol compound (b1) to the novolak phenol compound (b2) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, To 80/20, and particularly preferably 30/70 to 70/30. If the epoxy resin (A) is only the epoxy resin (a) containing an oxazolidone ring and the curing agent (B) is only a mixture of the bisphenol compound (b1) and the novolak phenol compound (b2), the effect of the present invention is maximized. Further, if the epoxy resin composition is contained in the combination in this combination, since the effect of the content is added as compared with the case where the epoxy resin composition is not contained, the addition amount of the epoxy resin composition may be a small amount.

The content of the oxazolidone ring-containing epoxy resin (a) in the epoxy resin (A) is preferably 5 to 100 mass%, more preferably 20 to 100 mass%, still more preferably 50 to 100 mass% To 100% by mass is particularly preferable, and 100% by mass is most preferable. The content of the mixture of the bisphenol compound (b1) and the novolak phenol compound (b2) in the curing agent (B) is preferably from 5 to 100 mass%, more preferably from 20 to 100 mass%, further preferably from 50 to 100 mass% , Particularly preferably 70 to 100 mass%, and most preferably 100 mass%. In the case of using a reaction product comprising an oxazolidone ring-containing epoxy resin (a) containing by-products or the like, when the content of the epoxy resin (a) containing an oxazolidin ring in the reaction product is remarkably small (for example, 20 mass% or less), the mass of the reaction product is preferably calculated as the mass of the epoxy resin (a) containing the oxazolidone ring.

The bisphenol compound (b1) is represented by the above formula (2). In formula (2), R ² independently represents a hydrogen atom, a halogen atom, a halogenated hydrocarbon group of 1 to 20 carbon atoms, or a carbon atom of 1 to 20 carbon atoms which may have a hetero atom. These are the same as those described for R ¹ in the formula (1). X ² is a cycloalkylidene group having 5 to 8 ring atoms and at least one hydrocarbon group having 1 to 20 carbon atoms as a substituent. These are the same as those described in X ¹ of the formula (1).

The bisphenol compound (b1) is obtained by reacting a corresponding phenolic compound with a cyclic aliphatic ketone. Specific examples of the bisphenol compound (b1) include a bisphenol compound containing a cycloalkylidene group as shown below, but the present invention is not limited thereto. In addition, the residue obtained by removing two hydroxyphenyl groups (which may have a substituent other than hydrogen) from the bisphenol compound is X ² , which is also preferable X ¹ . Similarly, the substituent substituting with two hydroxyphenyl groups is R ² , which is also a preferred R ¹ .

[Chemical Formula 8]

These exemplified cycloalkylidene group-containing bisphenol compounds can be produced, for example, by the method disclosed in JP-A-4-282334 or JP-A-2015-51935, but they are also available as commercial products, BisP-nBZ, bisOEP-2HBP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol-A, bisphenol- ) And the like. Among these, 4,4 '- (3,3,5-trimethylcyclohexylidene) bisphenol, 4,4' - (3,3,5,5-tetramethyl Cyclohexylidene) bisphenol are preferable, and 4,4 '- (3,3,5-trimethylcyclohexylidene) bisphenol is more preferable.

The novolak phenol compound (b2) is represented by the above formula (3). Is preferably represented by the above formula (4).

In formula (3), A ¹ independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups may be substituted with a substituent group (R ²⁰ ), and the aromatic ring group has at least one substituent (R ¹⁸ ). The substituent (R ¹⁸ ) is any of an aryl group having 6 to 48 carbon atoms, an aryloxy group having 6 to 48 carbon atoms, an aralkyl group having 7 to 49 carbon atoms, or an aralkyloxy group having 7 to 49 carbon atoms. Examples of the substituent (R ¹⁸ ) include a group represented by the above formula (4a), a phenyl group, a naphthyl group, an indanyl group, a 2-phenylethyl group, a naphthylmethyl group, an anthracenylmethyl group, a phenoxy group, a naphthyloxy group, Methyloxy group is preferable, and benzyl group and 1-phenylethyl group are more preferable. By having the substituent (R ¹⁸ ), the physical properties of the cured product can be improved.

The aromatic ring group constituting A ¹ may have another substituent (R ¹⁷ ) in addition to the essential substituent (R ¹⁸ ). Here, it is understood that the substituent (R ¹⁸ ) and the substituent (R ¹⁷ ) are one kind of substituent (R ²⁰ ). The hydrocarbon group having 1 to 49 carbon atoms which may have a hetero atom in the substituent (a1) is the same as the hydrocarbon group which may have a hetero atom described in R ¹ except that the number of carbon atoms is different. Substituents (R ¹⁸⁾ is R ⁸ and the substituents (R ¹⁷⁾ correspond to R ^7, however, reviews R ⁷ and R ⁸ is limited more as described in the formula (4) in the formula (4) .

The introduction of these substituents (R ¹⁸ ) can be obtained by subjecting phenols containing substituent (R ¹⁸ ) such as phenylphenol, cumylphenol, styrenated phenol, benzylphenol and phenoxyphenol as raw materials to novolak. In this case, it is the average value of the number of the substituent (R ¹⁸⁾ containing the substituent (R ¹⁸⁾ the number of the substituent (R ¹⁸⁾ as the phenol. When controlling the number of the substituent (R ¹⁸⁾ is, when used in combination is the substituted phenol-containing substituents than the substituent (R ¹⁸⁾ containing a phenol or a substituent (R ¹⁸⁾ of phenols and non-substituted.

The substituent (R ¹⁸ ) may also be introduced by using an aralkylating agent for the novolak phenol compound. In this case, the molar amount of the aralkylating agent to be used for one aromatic ring of the novolak phenol compound becomes the average value of the number of the substituent (R ¹⁸ ). The aralkylating agent is preferably added in an amount of 0.1 to 2.5 mols, more preferably 0.5 to 2.0 moles, and still more preferably 1.0 to 1.5 mols, per one aromatic ring of the novolak phenol compound.

Examples of the aralkylating agent include a phenylmethanol compound, a phenylmethyl halide compound, a naphthylmethanol compound, a naphthylmethyl halide compound, and a styrene compound. Specific examples thereof include benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, Chlorobenzyl chloride, 1-chloromethyl-2-naphthalene and nuclear substitution isomers thereof,? -Methylbenzyl chloride,?,? - methylbenzenesulfonyl chloride, Dimethylbenzyl chloride, benzyl methyl ether, o-methyl benzyl methyl ether, m-methyl benzyl methyl ether, p-methyl benzyl methyl ether, p-ethyl benzyl methyl ether and nuclear substitution isomers thereof, benzyl ethyl ether, Benzyl isobutyl ether, benzyl n-butyl ether, p-methyl benzyl methyl ether and nuclear substitution isomers thereof, benzyl alcohol, o-methyl benzyl alcohol, m- methyl benzyl alcohol, p- methyl benzyl alcohol, , p-tert-butylbenzyl alcohol, p-phenylbenzyl alcohol,? -naphthylmethanol and nuclear substitution isomers thereof,? -methylbenzyl alcohol,?,? - dimethylbenzyl alcohol, styrene, o -Methylstyrene, m-methylstyrene, p-methylstyrene,? -Methylstyrene,? -Methylstyrene and the like. The styrene compound may contain a small amount of another reaction component (for example, an unsaturated bond-containing component such as divinylbenzene, indene, coumarone, benzothiophene, indole, vinylnaphthalene, etc.). These may be used alone or in combination of two or more. Of these, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,? -Methylstyrene,? -Methylstyrene, benzylchloride and the like are preferable because they have excellent heat resistance and lower dielectric constant and dielectric tangent. , Benzyl bromide, or benzyl alcohol are preferable.

The reaction for introducing these aralkylating agents can be carried out in the presence of an acid catalyst. The acid catalyst may be appropriately selected from known inorganic and organic acids. For example, there may be mentioned mines such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethylsulfuric acid and diethylsulfuric acid, and organic acids such as zinc chloride, , And solid acids such as ion exchange resins, activated clay, silica-alumina, and zeolite.

Part of the hydroxyl group is converted into an aralkyloxy group by reacting the phenol novolak compound obtained by the reaction of the phenol with a bifunctional or higher functional group and a crosslinking group and the aralkylating agent in the presence of an alkali catalyst. Examples of the alkali catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and inorganic alkalis such as metal sodium, metal lithium, sodium carbonate and potassium carbonate. The amount thereof is preferably in the range of 1 to 2 moles per 1 mole of the aralkylating agent.

The substituent (R ¹⁸ ) may be an aryl group or an aryloxy group in addition to the above, but the introduction thereof may be carried out by using an aryl-substituted phenol such as phenylphenol or an aryloxy-substituted phenol such as phenoxyphenol There is a way.

T is a bivalent aliphatic cyclic hydrocarbon group or a bivalent crosslinking group represented by the formula (3a) or the formula (3b).

The divalent aliphatic cyclic hydrocarbon group preferably has 5 to 15 carbon atoms, more preferably 5 to 10 carbon atoms. Specific examples include a cycloalkylidene group having 5 to 12 carbon atoms and a divalent group including a condensed ring shown by the following structural formula, but the present invention is not limited thereto. The cycloalkylidene group having 5 to 12 carbon atoms may be different in the number of carbon atoms or ring atoms, and the description of the cycloalkylidene group described in X ² is referred to, except that the substituent is not essential.

[Chemical Formula 9]

In the formula (3a), R ³ and R ⁴ each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a hetero atom, but may be a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Of an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 20 carbon atoms. When an aromatic ring is present in these substituents, the aromatic ring may have a hydroxyl group as a substituent.

In the formula (3b), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group of 1 to 6 carbon atoms. A ² is an aromatic group comprising a benzene ring, a naphthalene ring or a biphenyl ring. These rings constituting A ² may be substituted with the same substituent as A ¹ .

k is 1 or 2, and represents the number of hydroxyl groups in the raw material phenols. m represents the number of repeats and is 1 to 20; The average value is 1.5 or more, preferably 1.7 to 10, more preferably 2.0 to 5.0, and still more preferably 2.2 to 4.0.

As the novolak phenol compound (b2), a phenol novolak compound having a substituent represented by the above formula (4) is preferable. In the formula (4), R ⁷ independently represents a hydrocarbon group having 1 to 6 carbon atoms, but a methyl group, a tert-butyl group, a phenyl group, and a cyclohexyl group are preferable, and a methyl group is more preferable. R ⁸ represents a substituent represented by the above formula (4a). p is an integer of 0 to 3, and the average value thereof is a number of 0.1 to 2.5, preferably 0.5 to 2.0, more preferably 1.0 to 1.5. q is an integer of 0 to 2, and the average value thereof is a number of 0 to 2, preferably 0 to 1. In addition, p + q is an average value of 0.1 to 3.

In the formula (4a), R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom, a methyl group, a tert-butyl group or a phenyl group, Is more preferable. It is more preferable that one of R ⁹ and R ¹⁰ is a hydrogen atom and the other is a methyl group. Specific examples of R ⁸ include a benzyl group, a methylbenzyl group, an ethylbenzyl group, an isopropylbenzyl group, a tert-butylbenzyl group, a cyclohexylbenzyl group, a phenylbenzyl group, a dimethylbenzyl group, A 2-phenylpropan-2-yl group, a 2-tolylpropan-2-yl group and a 2-xylylpropan-2-yl group.

As the phenol novolak compound represented by the formula (4), a styrene-modified novolak resin represented by the following formula (7) in which styrene is added to a phenol novolac resin is preferable. In formula (7), p and m correspond to p and m in formula (4).

[Chemical formula 10]

The raw phenols to be used for obtaining the novolac phenol compound (b2) include phenol, cresol, ethyl phenol, butyl phenol, phenyl phenol, styrenated phenol, cumyl phenol, benzyl phenol, phenoxy phenol, naphthol, Naphthalene diol, and the like. However, the present invention is not limited thereto. These phenols may be used alone, or two or more of them may be used in combination. Among these phenols, monophenols such as phenol and alkylphenol are preferable. As the alkyl group in the case of alkylphenol, an alkyl group having 1 to 6 carbon atoms is suitable. As described above, in the case of phenylphenol, cumylphenol, styrenated phenol, benzylphenol, or phenoxyphenol, the compound obtained by novolaking with a crosslinking agent is directly converted into the novolak phenol compound (b2). In the other cases, it is necessary to add substituents such as an aralkyl group containing an aromatic ring using an aralkylating agent or the like.

Examples of the crosslinking agent for imparting T in the formula (3) include aldehydes such as formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, amylaldehyde and benzaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone and acetophenone Ketones and p-xylylene glycol, dialkoxys such as p-xylylene glycol dimethyl ether, 4,4'-dimethoxymethylbiphenyl, dimethoxymethylnaphthalenes and the like, p-xylylene dichloride, 4,4'-dichloromethylbiphenyl, and dichloromethylnaphthalenes; divinyl compounds such as divinylbenzenes, divinylbiphenyls and divinylnaphthalenes; cyclopentadiene and dicyclopentadiene, and the like; But the present invention is not limited thereto. These crosslinking agents may be used alone or in combination of two or more. The T in the formula (3) becomes a bivalent aliphatic cyclic hydrocarbon group when a cycloalkadiene is used, and a crosslinking group represented by a formula (3a) when an aldehyde or a ketone is used, and a glycol, a dialkoxy, When a divinyl compound is used, it is a crosslinking group represented by the formula (3b). Of these crosslinking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, p-xylylene dichloride and 4,4'-dichloromethylbiphenyl are preferable, and formaldehyde is particularly preferable. Preferable forms when formaldehyde is used in the reaction include formalin aqueous solution, paraformaldehyde, and trioxane.

The molar ratio of the phenol and the crosslinking agent is represented by the molar ratio of the phenol to the 1 mole of the crosslinking agent (phenol / crosslinking agent) and the molar ratio is 0.1 or more. When the molar ratio is large, however, Is small, a high molecular weight substance having 5 or more nuclei is generated, and a number of 2-nuclei and 3-nuclei are decreased. Here, in the novolak phenol compound (b2) represented by the formula (3), the nucleus such as a bipole or a triple nucleus means the number of A ¹ existing in the molecule. That is, the i-core is a compound of the structural formula of m = i-1 in the formula (3). The molar ratio (phenol / crosslinking agent) between the phenol and the crosslinking agent is preferably 0.1 to 10, more preferably 0.3 to 6, still more preferably 0.5 to 4. In addition, novolak phenol compounds having a narrow molecular weight distribution can be obtained by reducing or eliminating low molecular weight components as necessary. In this case, as a method for reducing or removing a low-molecular-weight component, particularly a bipole, there may be mentioned a method using a difference in solubility of various solvents, a method dissolving in an aqueous alkali solution, and other known separation methods.

Examples of the acidic catalyst used for obtaining the novolak phenol compound (b2) include proton acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, and toluenesulfonic acid; Lewis acids such as boron trifluoride, aluminum chloride, tin chloride, , Oxalic acid, and monochloracetic acid. However, the present invention is not limited thereto. These acidic catalysts may be used alone or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid and oxalic acid are preferable.

The epoxy resin (A) in the epoxy resin composition of the present invention may be used in combination with an epoxy resin other than the oxazolidone ring-containing epoxy resin (a) within the range not deteriorating the physical properties. The epoxy resin other than the oxazolidone ring-containing epoxy resin (a) which can be used in combination is not particularly limited, and a polyfunctional epoxy resin containing two or more epoxy groups is preferable. Specific examples include polyglycidyl ether compounds, polyglycidylamine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins, but are not limited thereto. These epoxy resins may be used alone, or two or more of the same epoxy resins may be used in combination, or epoxy resins of different systems may be used in combination. The amount of the epoxy resin other than the oxazoline ring-containing epoxy resin (a) is 0 to 95% by mass, preferably 0 to 80% by mass, more preferably 0 to 50% by mass in the epoxy resin (A) , And more preferably 0 to 30 mass%.

Specific examples of the polyglycidyl ether compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, biphenol type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin , Naphthalene diol type epoxy resin, bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, resorcinol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Naphthalene novolac epoxy resin, naphthalene aralkyl type epoxy resin, naphthalene diol aralkyl type epoxy resin, alpha -naphthol aralkyl type epoxy resin, aromatic naphthalene type epoxy resin, Type epoxy resin, a biphenylaralkylphenol type epoxy resin, a trihydroxyphenylmethane type epoxy resin , Tetrahydroxyphenyl ethane type epoxy resin, dicyclopentadiene type epoxy resin, alkylene glycol type epoxy resin, aliphatic cyclic epoxy resin, and the like, but are not limited thereto.

Specific examples of the polyglycidylamine compound include diaminodiphenylmethane type epoxy resin, meta xylene diamine type epoxy resin, 1,3-bisaminomethylcyclohexane type epoxy resin, isocyanurate type epoxy resin, Aniline type epoxy resin, hydantoin type epoxy resin, and aminophenol type epoxy resin. However, the present invention is not limited thereto.

Specific examples of the polyglycidyl ester compound include dimer acid type epoxy resins, hexahydrophthalic acid type epoxy resins, trimellitic acid type epoxy resins and the like, but are not limited thereto.

Examples of the alicyclic epoxy compound include alicyclic epoxy resins such as Celloxide 2021 (manufactured by Daicel Chemical Industries, Ltd.) and the like, but are not limited thereto.

Specific examples of other modified epoxy resins include urethane-modified epoxy resins, epoxy resins containing an oxazolidone ring having a skeleton other than (a), epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins, polyvinylarylene polyoxides For example, divinylbenzene dioxide, trivinylnaphthalene trioxide and the like), and phosphorus-containing epoxy resins, but are not limited thereto.

The curing agent (B) in the epoxy resin composition of the present invention may be used in combination with a curing agent other than the bisphenol compound (b1) and the novolak phenol compound (b2) within the range not impairing the physical properties. The curing agent other than (b1) and (b2) which can be used in combination is not particularly limited and is not particularly limited as long as it can cure the epoxy resin, and examples thereof include phenol series curing agents, acid anhydride series curing agents, amine series curing agents, A curing agent for an epoxy resin such as a curing agent, an active ester curing agent, and a phosphorus-containing curing agent can be used. These curing agents may be used alone, or two or more of the same curing agents may be used in combination, or different curing agents may be used in combination. The amount of the curing agent other than (b1) and (b2) is 0 to 95 mass%, preferably 0 to 80 mass%, more preferably 0 to 50 mass%, and more preferably 0 to 30 mass% in the curing agent (B) % Is more preferable.

As the phenol-based curing agent, those containing a large amount of an aromatic skeleton in the molecular structure are preferable, and examples thereof include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, phenol aralkyl resins, Cresol novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins can be cited as examples of the novolak resin. Of these, the same as in the above formula (3) is considered to be (b2), and therefore, an unsubstituted compound, an alkyl substituent, a cycloalkyl substituent or an alkyloxy substituent is preferable.

Also, a benzoxazine photographic compound which is opened upon heating to form a phenol compound is also useful as a curing agent. Specific examples thereof include benzooxazine compounds of bisphenol F type or bisphenol S type, but are not limited thereto.

Specific examples of the acid anhydride-based curing agent include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, hydrogenated trimellitic acid anhydride, Acid, anhydrous succinic acid, maleic anhydride and the like, 4,4'-oxydiphthalic anhydride, 4,4'-biphthalic anhydride, anhydrous pyromellitic acid, hydrogenated pyromellitic anhydride, 1,2,3,4- Cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic acid anhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and the like But the present invention is not limited thereto.

Examples of the amine-based curing agent include amine compounds usable as the above-mentioned various epoxy resin modifiers. In addition to the above, amine compounds such as 2,4,6-tris (dimethylaminomethyl) phenol, dimer diamine, dicyandiamide and its derivatives, and polyamines which are condensates of polyamines with acids such as dimer acid But the present invention is not limited thereto.

Specific examples of the hydrazide-based curing agent include, but are not limited to, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide and dodecane dihydric dihydrazide .

Examples of the active ester type curing agent include reaction products of a polyfunctional phenolic compound and an aromatic carboxylic acid described in Japanese Patent No. 5152445, and commercially available products include Epiclon HPC-8000-65T (manufactured by DIC Co., Ltd.) and the like But are not limited thereto.

The ratio of the epoxy resin (A) to the curing agent (B) is preferably 0.2 to 1.5 moles of the active hydrogen group of the curing agent (B) relative to 1 mole of the epoxy group of the epoxy resin (A). When the active hydrogen group is less than 0.2 mole or more than 1.5 mole based on 1 mole of the epoxy group, the curing becomes incomplete and there is a possibility that good cured properties are not obtained. The preferred range is 0.3 to 1.5 moles, the more preferred range is 0.5 to 1.5 moles, and the more preferable range is 0.8 to 1.2 moles. The amount of the bisphenol compound (b1) and the novolac (b1) relative to 1 mole of the epoxy group of the epoxy resin (a) containing the oxazolidone ring or the reaction product (a2) containing the oxazololidone ring- The total amount of the phenolic hydroxyl groups in the phenol compound (b2) is preferably from 0.8 to 1.2 mols, more preferably from 0.9 to 1.1 mols, and still more preferably from 0.95 to 1.05 mols. When an epoxy resin other than the epoxy resin (a) containing the oxazolidone ring or the reaction product (a2) or a curing agent other than the bisphenol compound (b1) and the novolak phenol compound (b2) is used in combination in the epoxy resin composition, It is preferable to determine the blending amount after adding the optimal blending amount of the epoxy resin or the curing agent to be used in combination. For example, when a phenol-based curing agent, an amine-based curing agent, or an active ester-based curing agent is used in combination, the active hydrogen group is approximately equimolarly added to the epoxy group, and when an acid anhydride-based curing agent is used in combination, an acid anhydride group of 0.5 To 1.2 moles, preferably 0.6 to 1.0 moles.

As used herein, the term "active hydrogen group" refers to a functional group having an active hydrogen reactive with an epoxy group (including a functional group having a latent active hydrogen for generating active hydrogen by hydrolysis or the like, or a functional group exhibiting an equivalent curing action) Include an acid anhydride group, a carboxyl group, an amino group, and a phenolic hydroxyl group. Further, regarding the active hydrogen group, the carboxyl group (-COOH) and the phenolic hydroxyl group (-OH) are calculated as 1 mole, and the amino group (-NH ₂ ) is calculated as 2 mole. When the active hydrogen group is not clear, the active hydrogen equivalent can be obtained by measurement. For example, by reacting a monoepoxy resin having an epoxy equivalent, such as phenyl glycidyl ether, and a curing agent whose active hydrogen equivalent is unknown, and measuring the amount of monoepoxy resin consumed, the active hydrogen equivalent of the curing agent used is obtained .

In the epoxy resin composition of the present invention, a curing accelerator may be used if necessary. Examples of the curing accelerator include, but are not limited to, phosphorus compounds such as imidazole derivatives, tertiary amines and phosphines, metal compounds, Lewis acids, and amine complexes. These curing accelerators may be used alone or in combination of two or more.

The imidazole derivative may be any compound having an imidazole skeleton, and is not particularly limited. Ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl- Alkyl substituted imidazole compounds such as 2-phenylimidazole, 2-phenylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole and 2-heptadecylimidazole, Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2- phenylimidazole, benzimidazole, Substituted with a hydrocarbon group containing a cyclic structure such as an aryl group or an aralkyl group such as - (2'-cyanoethyl) imidazole, 2,3-dihydro-1H-pyrrolo [ Imidazole compounds, and the like, but are not limited thereto.

Examples of the tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene ), But the present invention is not limited thereto.

Examples of the phosphine include, but are not limited to, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, and the like.

The metal compound includes, for example, tin octylate, but is not limited thereto.

Examples of the amine complex salt include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride benzylamine complex, boron trifluoride A boron trifluoride complex such as an aniline complex or a mixture thereof, and the like, but the present invention is not limited thereto.

Among these curing accelerators, 2-dimethylaminopyridine, 4-dimethylaminopyridine and imidazoles are preferable from the standpoint of heat resistance, dielectric properties, solderability and the like when they are used for build-up material applications or circuit board applications . When used as a semiconductor encapsulating material, triphenylphosphine and DBU are preferable because they are excellent in curability, heat resistance, electrical properties, moisture resistance and the like.

The blending amount of the curing accelerator may be appropriately selected according to the purpose of use, but 0.01 to 15 parts by mass relative to 100 parts by mass of the epoxy resin component in the epoxy resin composition is used if necessary. The amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, still more preferably 0.1 to 5 parts by mass. By using the curing accelerator, it is possible to lower the curing temperature and shorten the curing time.

As the epoxy resin composition, an organic solvent or a reactive diluent may be used for adjusting the viscosity.

Examples of the organic solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, amides such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol Ethers such as diethyl ether and triethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as methanol, ethanol, 1-methoxy- But are not limited to, alcohols such as 1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diglycol and pine oil, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diglycol acetate, Acetic acid esters such as monomethyl ether acetate, carbitol acetate and benzyl alcohol acetate, benzoic acid esters such as methyl benzoate and ethyl benzoate , Cellosolves such as methyl cellosolve, cellosolve and butyl cellosolve, carbitols such as methyl carbitol, carbitol and butyl carbitol, aromatic hydrocarbons such as benzene, toluene and xylene, Sodium, acetonitrile, N-methylpyrrolidone, and the like, but are not limited thereto.

Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and tolyl glycidyl ether, Resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, Bifunctional glycidyl ethers such as propylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylol propane polyglycidyl ether, trimethylol ethane polyglycidyl ether, pentaerythritol polyglycidyl ether , Glycidyl esters such as neodecanoic acid glycidyl ester, and glycidyl amines such as phenyl diglycidyl amine and tolyldiglycidyl amine. Among these, glycidyl ethers such as poly Limited It is not.

These organic solvents or reactive diluents are preferably used singly or as a mixture of plural kinds in an amount of not more than 90% by mass as nonvolatile components, and the appropriate kinds and amounts thereof to be used are appropriately selected according to the use. For example, in the case of a printed wiring board, it is preferably a polar solvent having a boiling point of 160 DEG C or less such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, and the amount thereof is 40 to 80 mass% desirable. In the application of the adhesive film, it is preferable to use, for example, ketones, acetic acid esters, carvitol, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N- The volatile content is preferably 30 to 60% by mass.

For the purpose of improving the flame retardancy of the resulting cured product, various flame retardants known to those skilled in the art can be used in the epoxy resin composition within a range not lowering the reliability. Examples of the flame retardant which can be used include halogen-based flame retardants, phosphorus flame retardants (phosphorus compounds as flame retardants), nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants and organometallic salt-based flame retardants. From the viewpoint of the environment, a halogen-free flame retardant is preferable, and a phosphorus flame retardant is particularly preferable. These flame retardants are not particularly limited at the time of use, and they may be used alone, or a plurality of flame retardants may be used in combination, or flame retardants of different types may be used in combination.

As the phosphorus-containing additive, any of an inorganic phosphorus compound and an organic phosphorus compound may be used. Examples of the inorganic phosphorus compound include, but are not limited to, ammonium nitrogen compounds such as ammonium monophosphate, ammonium dihydrogen phosphate, ammonium triphosphate, ammonium polyphosphate, and phosphorous acid inorganic phosphorus compounds such as phosphoric acid amide no.

Examples of the organophosphorous compound include general organic phosphorus compounds such as phosphoric acid ester compounds, condensed phosphoric acid esters, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds and phosphoric acid compounds, (For example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide, etc.) having an active hydrogen group directly connected to a phosphorus atom ) Or a phosphorus containing phenol compound (for example, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10- Oxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxinaphthalene, 1,4-cyclooctylene Phosphino-1,4-phenyldiol, 1,5-cyclooctylenephenylphosphinyl-1,4-phenyldiol) and the like, A compound reacting that derivative group such as an epoxy or phenolic resin, a phosphorus-based compound, but is not limited to these.

Examples of the phosphorus-containing epoxy resin that can be used in combination include Epotoft FX-305, FX-289B, TX-1320A and TX-1328 (manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.) But is not limited thereto. The epoxy equivalent of the phosphorus-containing epoxy resin that can be used is preferably 200 to 800, more preferably 300 to 780, and still more preferably 400 to 760. The phosphorus content is preferably 0.5 to 6% by mass, more preferably 2 to 5.5% by mass, and still more preferably 3 to 5% by mass. As the phosphorus-containing curing agent that can be used in combination, in addition to the phosphorus-containing phenol compound described above, a phosphorus compound is reacted with an aldehyde and a phenol compound by the production method as disclosed in Japanese Patent Application Publication No. 2008-501063 or Japanese Patent No. 4548547 To obtain a phosphorus-containing phenol compound. In addition, a phosphorus-containing active ester compound can be obtained from a phosphorus-containing phenol compound by reacting an aromatic carboxylic acid with a production method as disclosed in JP-A-2013-185002. In addition, a phosphorus-containing benzoxazine photographic compound can be obtained by a production method as described in WO2008 / 010429.

The compounding amount of the phosphorus compound to be used in combination is appropriately selected depending on the kind of the phosphorus compound, the phosphorus content, the component of the epoxy resin composition, and the degree of desired flame retardancy. (Non-volatile matter) in the epoxy resin composition in which the phosphorus compound is a reactive phosphorus compound, that is, the phosphorus-containing epoxy resin or the phosphorus-containing curing agent, the epoxy resin, the curing agent for the epoxy resin, the flame retardant, The phosphorus content is preferably 0.2 to 6 mass% or less, more preferably 0.4 to 4 mass% or less, still more preferably 0.5 to 3.5 mass% or less, and particularly preferably 0.6 to 3.0 mass% or less. If the phosphorus content is low, there is a fear that the flame retardancy can not be ensured, and if it is too much, the heat resistance may be adversely affected. When the phosphorus compound is an addition-type phosphorus-based flame retardant, it is preferably blended in an amount of 0.1 to 2 parts by mass in the case of using 100 parts by mass of the solid content (non-volatile fraction) in the epoxy resin composition, It is preferably blended in the range of 0.1 to 10 parts by mass, particularly preferably in the range of 0.5 to 6 parts by mass.

When a phosphorus compound is used as the flame retardant, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, calcium carbonate, zinc molybdate, or the like may be used in combination as the flame retardant aid.

In the present invention, a phosphorus compound is preferably used as the flame retardant, but the flame retardant described below may also be used.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable . The amount of the nitrogen-based flame retardant to be blended is appropriately selected according to the kind of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the degree of desired flame retardancy. For example, By mass, particularly preferably within a range of 0.1 to 5 parts by mass. When a nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound or the like may be used in combination.

As the silicon-based flame retardant, an organic compound containing a silicon atom can be used without particular limitation, and examples thereof include silicone oil, silicone rubber, and silicone resin, but are not limited thereto. The blending amount of the silicon-based flame retardant is appropriately selected according to the kind of the silicon-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, 0.05 to 20 parts by mass of 100 parts by mass of the solid component (nonvolatile component) It is preferable to blend it in the range. When a silicone flame retardant is used, a molybdenum compound or alumina may be used in combination.

Examples of the inorganic flame retardant include, but are not limited to, metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glass. The blending amount of the inorganic flame retardant is appropriately selected according to the kind of the inorganic flame retardant, the other components of the epoxy resin composition, and the degree of desired flame retardancy, and for example, all of epoxy resin, curing agent for epoxy resin, flame retardant, Is preferably compounded in a range of 0.05 to 20 parts by mass, more preferably 0.5 to 15 parts by mass in 100 parts by mass of a solid content (non-volatile matter) in one epoxy resin composition.

Examples of the organic metal salt-based flame retardant include ferrocene, an acetylacetonate metal complex, an organic metal carbonyl compound, an organic cobalt salt compound, an organic sulfonic acid metal salt, a compound in which a metal atom and an aromatic compound or a heterocyclic compound are ionically or coordinately bonded But the present invention is not limited thereto. The blending amount of the organometallic salt-based flame retardant is appropriately selected according to the kind of the organometallic salt-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy, and examples thereof include epoxy resins, curing agents for epoxy resins, Is preferably added in the range of 0.005 to 10 parts by mass based on 100 parts by mass of the solid content (non-volatile component) of the epoxy resin composition containing all of the above components.

The epoxy resin composition may contain a filler, a thermoplastic resin, a thermosetting resin other than an epoxy resin, a silane coupling agent, an antioxidant, a releasing agent, a defoaming agent, an emulsifier, a thixotropic agent, a smoothing agent, And other additives may be added.

Examples of the filler include fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, bayite, talc, mica, clay, calcium carbonate, magnesium carbonate, Inorganic fillers such as titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate and carbon, carbon fillers such as carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber and aramid fiber , A ceramic filler such as a ceramic fiber, and a particulate rubber. Among them, those which are not decomposed or dissolved by an oxidizing compound such as an aqueous solution of a permanganate used in the surface roughening treatment of the cured product are preferred, and fused silica and crystalline silica are particularly preferable since fine particles are easily obtained. When the blending amount of the filler is made particularly large, fused silica is preferably used. The fused silica may be either crushed or spherical. However, in order to increase the amount of the fused silica and suppress the increase of the melt viscosity of the molding material, it is more preferable to use a spherical one. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filler may be treated with a silane coupling agent or an organic acid such as stearic acid. In general, the reason for using the filler is to improve the impact resistance of the cured product and to lower the thermal expansion of the cured product. Further, when a metal hydroxide such as aluminum hydroxide, bainite, or magnesium hydroxide is used, it acts as a flame retardant adjuvant and has an effect of improving flame retardancy. When it is used for a conductive paste or the like, a conductive filler such as silver powder or copper powder can be used.

The blending amount of the filler is preferably high in consideration of low linear expansion of the cured product and flame retardancy. Is preferably from 1 to 90 mass%, more preferably from 5 to 80 mass%, and even more preferably from 10 to 60 mass%, based on the solid content (nonvolatile content) in the epoxy resin composition. If the blending amount is large, there is a fear that the adhesiveness required for the laminated board application is lowered, and the cured product is disengaged, so that sufficient mechanical properties can not be obtained. If the compounding amount is too small, there is a possibility that the effect of compounding of the filler, such as improvement of the impact resistance of the cured product, may not be exhibited.

The average particle diameter of the inorganic filler is preferably 0.05 to 1.5 占 퐉, more preferably 0.1 to 1 占 퐉. When the average particle diameter of the inorganic filler is within this range, the fluidity of the epoxy resin composition can be maintained satisfactorily. The average particle size can be measured by a particle size distribution measuring apparatus.

The blending of the thermoplastic resin is particularly effective when the epoxy resin composition is molded into a sheet or a film. Examples of the thermoplastic resin include phenoxy resin, polyurethane resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, vinyl chloride resin, polyvinyl acetate resin, polymethyl methacrylate A resin, a polycarbonate resin, a polyacetal resin, a cyclic polyolefin resin, a polyamide resin, a thermoplastic polyimide resin, a polyamideimide resin, a polytetrafluoroethylene resin, a polyetherimide resin, a polyphenylene ether resin, A polyether sulfone resin, a polyether sulfone resin, a polyether ether ketone resin, a polyphenylene sulfide resin, a polyvinyl formal resin, and the like, but is not limited thereto. From the viewpoint of compatibility with the epoxy resin, phenoxy resin is preferable, and from the viewpoint of low dielectric property, polyphenylene ether resin and modified polyphenylene ether resin are preferable.

Examples of other additives include thermosetting resins other than epoxy resins such as phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, diallyl phthalate resin and thermosetting polyimide, quinacridone resin, Organic pigments such as phthalocyanine pigments, inorganic pigments such as titanium oxide, metal foil pigments and antirust pigments, ultraviolet absorbers such as hindered amine, benzotriazole and benzophenone, hindered phenol, phosphorus, sulfur, An antioxidant such as a hydrazide-based agent, a coupling agent such as a silane-based or titanium-based coupling agent, a releasing agent such as stearic acid, palmitic acid, zinc stearate, calcium stearate, a leveling agent, a rheology control agent, An antifogging agent, an anti-cratering agent, and an antifoaming agent. The blending amount of these other additives is preferably in the range of 0.01 to 20 mass% with respect to the solid content (nonvolatile content) in the epoxy resin composition.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above components. The cured product of the present invention can be easily obtained by curing in the same manner as a conventionally known method. As a method for obtaining the cured product, the same method as the known epoxy resin composition can be employed, and a method such as a mold, injection, potting, dipping, drip coating, transfer molding, compression molding, Legs or the like, followed by heating and pressure-curing to form a laminated board. The curing temperature at that time is usually in the range of 100 to 300 占 폚, and the curing time is usually about 10 minutes to 5 hours. Examples of the cured product include molded cured products such as a laminate, a mold, a molded product, an adhesive layer, an insulating layer, and a film.

Examples of applications in which the epoxy resin composition is used include circuit board materials, sealing materials, mold materials, conductive pastes, adhesives, and the like. Examples of the material for a circuit board include prepregs, resin sheets, metal foils on which a resin is formed, resin compositions for printed wiring boards and flexible wiring boards, insulating materials for circuit boards such as interlayer insulating materials for build-up boards, Ink, and the like. Among these various applications, in the use of a printed wiring board material, an insulating material for a circuit board, and an adhesive film for a build-up, a so-called insulating material for a board for incorporating electronic components, in which passive components such as capacitors and active parts such as IC chips are embedded in a substrate . Among them, a material for a circuit board (laminated board) such as a printed wiring board material, a resin composition for a flexible wiring board, an interlayer insulating material for a build-up substrate, and a semiconductor It is preferable to use it for an encapsulating material.

When the epoxy resin composition is formed into a plate shape such as a laminated plate, the filler to be used is preferably fibrous in view of dimensional stability and bending strength, and more preferably a glass cloth, a glass mat, or a glass roving cloth.

The epoxy resin composition can be impregnated with a fibrous reinforcing base material to prepare a prepreg for use as a printed wiring board or the like. As the fibrous reinforcing base material, inorganic fibers such as glass, woven or nonwoven fabric of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, aromatic polyamide resin and the like can be used, no.

The method for producing the prepreg from the epoxy resin composition is not particularly limited, and for example, the epoxy resin composition on the varnish containing the above-mentioned organic solvent may be mixed with an organic solvent to prepare a resin varnish , Impregnating the resinous varnish with the fibrous substrate, and heating and drying the resin varnish to semi-cure (B-staged) the resin component. The heating temperature is preferably 50 to 200 占 폚, more preferably 100 to 170 占 폚, depending on the kind of the organic solvent used. The heating time is preferably 1 to 40 minutes, and more preferably 3 to 20 minutes, depending on the type of the organic solvent used and the curing property of the prepreg. At this time, the mass ratio of the epoxy resin composition to the reinforcing base material to be used is not particularly limited, but is preferably adjusted so that the amount of resin in the prepreg is 20 to 80% by mass.

The epoxy resin composition of the present invention can be molded into a sheet or a film. In this case, they can be formed into a sheet or a film using a conventionally known method. The method for producing the resin sheet is not particularly limited. For example, a resin varnish is applied onto a support base film which is not dissolved in the resin varnish by using a coater such as a reverse roll coater, a comma coater, a die coater Followed by heating and drying to make the resin component B-staged. If necessary, a separate support base film is laminated as a protective film on the application surface (adhesive layer) and dried to obtain an adhesive sheet having a release layer on both surfaces of the adhesive layer.

Examples of the support base film include a metal foil such as copper foil, a polyolefin film such as a polyethylene film and a polypropylene film, a polyester film such as a polyethylene terephthalate film, a polycarbonate film, a silicon film and a polyimide film. Among them, a polyethylene terephthalate film having no defects such as granules and excellent in dimensional accuracy and excellent in cost is preferable. Further, a metal foil, particularly a copper foil, which facilitates multilayering of the laminated board is preferable. The thickness of the support base film is not particularly limited, but is preferably from 10 to 150 占 퐉, more preferably from 25 to 50 占 퐉, in view of strength as a support and difficulty in causing lamination failure.

The thickness of the protective film is not particularly limited, but is generally from 5 to 50 탆. Further, in order to easily peel off the formed adhesive sheet, it is preferable to carry out surface treatment with a release agent in advance. The thickness of the resin varnish to be applied is preferably 5 to 200 占 퐉, more preferably 5 to 100 占 퐉 in terms of the thickness after drying. The heating temperature is preferably 50 to 200 占 폚, more preferably 100 to 170 占 폚, depending on the kind of the organic solvent used. The heating time is preferably 1 to 40 minutes, and more preferably 3 to 20 minutes, depending on the type of the organic solvent used and the curing property of the prepreg.

The resin sheet thus obtained is usually an insulating adhesive sheet having insulating properties, but a conductive adhesive sheet can also be obtained by mixing a metal having conductivity or a metal-coated microparticle with the epoxy resin composition. Further, the support base film is peeled off after the insulating layer is formed by laminating on the circuit board or by heating and curing. When the support base film is peeled off after the adhesive sheet is heated and cured, adhesion of dust or the like in the curing process can be prevented. Here, the insulating adhesive sheet is also an insulating sheet.

The metal foil on which the resin obtained by the epoxy resin composition is formed will be described. The metal foil may be a single metal, alloy, or composite metal foil of copper, aluminum, mineral oil, nickel, or the like. It is preferable to use a metal foil having a thickness of 9 to 70 mu m. The flame retardant resin composition comprising the phosphorus-containing epoxy resin and the method for producing the metal foil on which the resin is formed from the metal foil are not particularly limited. For example, a resin obtained by adjusting the viscosity of the epoxy resin composition with a solvent The varnish can be obtained by applying the varnish using a roll coater or the like, followed by heating and drying to half-cure (B-stage) the resin component to form a resin layer. When the resin component is semi-cured, it can be heated and dried, for example, at 100 to 200 ° C for 1 to 40 minutes. The thickness of the resin portion of the metal foil on which the resin is formed is preferably 5 to 110 mu m.

In order to cure the prepreg or the insulating adhesive sheet, a curing method of a laminated board in manufacturing a printed wiring board is generally used, but the present invention is not limited thereto. For example, in the case of using a prepreg to form a laminate, a laminate is formed by laminating one or a plurality of prepregs and arranging a metal foil on one or both sides, and the laminate is heated under pressure to form a prepreg Cured and integrated to obtain a laminated board. As the metal foil, copper, aluminum, olive oil, nickel or the like alone, alloy, or composite metal foil may be used.

The conditions under which the laminate is heated and pressed can be appropriately adjusted under the condition that the epoxy resin composition is cured and heated and pressed. However, if the amount of pressure applied is excessively low, bubbles remain in the resulting laminate, Therefore, it is preferable to pressurize under the condition that the moldability is satisfied. The heating temperature is preferably 160 to 250 占 폚, more preferably 170 to 220 占 폚. The pressing pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if it is high, the cured product may be thermally decomposed. If the pressing pressure is low, bubbles may remain in the obtained laminated plate, resulting in deterioration of electrical characteristics. If the pressing pressure is high, the resin may flow before curing and there is a possibility that a laminated plate having a desired thickness may not be obtained. If the heating and pressurizing time is short, there is a fear that the curing reaction will not proceed sufficiently, and there is a fear that thermal decomposition of the cured product will take place on a long side.

Further, a multi-layered plate can be produced using the thus obtained single-layered laminate as an inner layer material. In this case, circuit formation is first performed on the laminate by the additive method or the subtractive method, and the surface of the formed circuit is treated with an acid solution to be blackened to obtain an inner layer material. An insulating layer is formed of a metal foil having a prepreg, a resin sheet, an insulating adhesive sheet or a resin on one surface or both circuit surfaces of the inner layer material, and a conductor layer is formed on the surface of the insulating layer to form a multi- will be.

In the case of forming the insulating layer by using the prepreg, one laminate of prepregs or a plurality of prepregs is disposed on the circuit formation surface of the inner layer material, and a metal foil is arranged on the outer side thereof to form a laminate. Then, the laminate is heated and pressed to integrally form a cured product of the prepreg as an insulating layer, and the metal foil on the outside of the prepreg is formed as a conductor layer. Here, as the metal foil, the same materials as those used for the laminate used as the inner layer material can be used. The heat press molding can be carried out under the same conditions as the molding of the inner layer material. A via hole or a circuit is formed on the surface of the multilayer laminate thus formed by the additive method or the subtractive method to form a printed wiring board. Further, by repeating the above-mentioned method using the printed wiring board as an inner layer material, a multilayered multilayered plate can be formed.

For example, in the case of forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is disposed on a circuit forming 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, the laminate is heated and pressed to be integrally formed, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multilayer of the inner layer material. Or a cured product of the insulating adhesive sheet is formed as an insulating layer between the inner layer material and the metal foil as the conductor layer. Here, as the metal foil, the same materials as those used for the laminate used as the inner layer material can be used. The heat press molding can be carried out under the same conditions as the molding of the inner layer material.

When the epoxy resin composition is applied to the laminate to form the insulating layer, the epoxy resin composition is preferably applied at a thickness of 5 to 100 탆, and then is dried at 100 to 200 캜, preferably at 150 to 200 캜 , For 1 to 120 minutes, preferably 30 to 90 minutes, to form a sheet. Is generally formed by a method called a casting method. The thickness after drying is preferably 5 to 150 占 퐉, preferably 5 to 80 占 퐉. The viscosity of the epoxy resin composition is preferably in the range of 10 to 40,000 mPa · s at 25 ° C, more preferably in the range of 200 to 30000 mPa · s at 25 ° C since a sufficient film thickness is obtained and coating irregularity and streaks are unlikely to occur mPa · s. A via-hole or a circuit is formed on the surface of the multilayer laminate thus formed by the additive method or the subtractive method to form a printed wiring board. Further, by repeating the above-mentioned method using the printed wiring board as an inner layer material, a multilayer laminate can be formed.

As the encapsulating material obtained by using the epoxy resin composition of the present invention, there can be used for a semiconductor chip on a tape, a potting liquid encapsulation, an underfill, an interlayer insulating film of a semiconductor, and the like. For example, in the semiconductor package molding, a method of molding a molded product by molding the epoxy resin composition using a mold, a transfer molding machine, an injection molding machine, etc., and heating at 50 to 200 DEG C for 2 to 10 hours .

In order to prepare the epoxy resin composition for the semiconductor encapsulating material, the epoxy resin composition is preliminarily mixed with an additive such as inorganic filler, coupling agent, mold releasing agent, and the like mixed as required, and then the mixture is extruded, kneaded, And the mixture is melt-mixed sufficiently until it becomes homogeneous. At this time, as the inorganic filler, silica is usually used, but in that case, it is preferable to blend the inorganic filler in an amount of 70 to 95 mass% in the epoxy resin composition.

When the epoxy resin composition thus obtained is used as an encapsulating material on a tape, the encapsulating material tape is heated to produce a semi-cured sheet, and the encapsulating material tape is placed on a semiconductor chip. Deg.] C, softening and molding, and completely curing at 170 to 250 [deg.] C. When used as a potting liquid encapsulant, the obtained epoxy resin composition may be dissolved in a solvent as required, and then applied to a semiconductor chip or an electronic part and directly cured.

The epoxy resin composition of the present invention can also be used as a resist ink. In this case, a composition for a resist ink is prepared by mixing a vinyl-based monomer having an ethylenically unsaturated double bond and a cation polymerization catalyst as a curing agent, and further adding a pigment, a talc and a filler to the epoxy resin composition, A method in which the composition is coated on a printed substrate by a printing method, and then a resist ink is cured. The curing temperature at this time is preferably in the range of about 20 to 250 ° C.

The epoxy resin composition of the present invention was prepared, and the cured product was evaluated by heat curing. As a result, it was possible to obtain a cured product having excellent balance of heat resistance, adhesiveness, and the like while exhibiting low dielectric properties. In addition, by blending a flame retardant agent, flame retardancy could be imparted without deteriorating heat resistance, adhesiveness and the like while exhibiting low dielectric properties.

Example

The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited thereto unless it is beyond the gist thereof. Unless otherwise stated, parts represent parts by mass, and% represents mass%.

The analysis method and the measurement method are shown below.

(1) Epoxy equivalent: It was in conformity with JIS K7236 standard.

(2) Softening point: Measured according to JIS K7234 standard, ring method. Specifically, an automatic softening point device (ASP-MG4, manufactured by Meitec Co., Ltd.) was used.

(3) Glass transition temperature: IPC-TM-650 DSC (manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR6000DSC6200 manufactured by Hitachi High-Tech Science Co., Ltd.) Tgm (intermediate temperature of the transition curve for the tangent line between the glassy state and the rubbery state).

(4) Copper peel strength and interlaminar adhesion: Measured according to JIS C6481 standard, and the interlaminar adhesive strength was peeled off between the 7th and 8th layers.

(5) Specific dielectric constant and dielectric tangent: The permittivity and the dielectric tangent at a frequency of 1 GHz were determined by a capacitance method using a METALIAL ANALYZER (AGILENT Technologies) according to IPC-TM-650 2.5.5.9 standard .

(6) Flame retardancy: Evaluated according to UL94 by the vertical method. The evaluation is described as V-0, V-1, and V-2.

Synthesis Example 1

TX-1468 (epoxy resin represented by the formula (5), epoxy equivalent 219, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.) was added to a glass separable flask equipped with a stirrer, a thermometer, a nitrogen gas introducing device, And 0.11 part of tetramethylammonium iodide were charged, the temperature was raised while nitrogen gas was supplied, and the temperature was maintained at 120 占 폚 for 30 minutes to remove water in the system. Next, 11.5 parts of diphenylmethane diisocyanate (NCO concentration: 34%) was added dropwise over 3 hours while being heated to 60 占 폚 while maintaining the reaction temperature at 130 占 폚 to 140 占 폚. After completion of dropwise addition, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (Resin 1). The obtained resin 1 had an oxazolidone ring modification ratio (Rox) of 0.2, an epoxy equivalent of 300, and a softening point of 85 캜.

Synthesis Example 2

100 parts of TX-1468 and 0.12 parts of tetramethylammonium iodide were charged into the same apparatus as in Synthesis Example 1, the temperature was raised while nitrogen gas was supplied, and the temperature was maintained at 120 占 폚 for 30 minutes to remove water in the system . Next, a mixture of tolylene diisocyanate (mixture of 2,4-tolylene diisocyanate (80%) and 2,6-tolylene diisocyanate (20%), NCO concentration of 48%) was added while maintaining the reaction temperature at 140 ° C to 150 ° C, 17.8 parts were added dropwise over 5 hours. After completion of the dropwise addition, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (Resin 2). The obtained resin 2 had a modification ratio (Rox) of 0.45, an epoxy equivalent of 464, and a softening point of 125 占 폚.

Synthesis Example 3

100 parts of TX-1468 and 0.12 parts of tetramethylammonium iodide were charged into the same apparatus as in Synthesis Example 1, the temperature was raised while nitrogen gas was supplied, and the temperature was maintained at 120 占 폚 for 30 minutes to remove water in the system . Next, 16.0 parts of cyclohexane-1,3-diylbis methylene diisocyanate (NCO concentration 43%) was added dropwise over 5 hours while maintaining the reaction temperature at 140 ° C to 150 ° C. After completion of the dropwise addition, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (Resin 3). The obtained resin 3 had a degree of modification (Rox) of 0.36, an epoxy equivalent of 400, and a softening point of 115 캜.

The content (mass%) of the unreacted epoxy resin is 49% for Resin 1, 20% for Resin 2, and 33% for Resin 3.

Synthesis Example 4

In the same apparatus as in Synthesis Example 1, 91 parts of 4,4 '- (4-methylcyclohexylidene) diphenol, 358 parts of epichlorohydrin, and 4 parts of ion-exchanged water were charged, Lt; / RTI > After uniformly dissolving, 5.3 parts of a 49% sodium hydroxide aqueous solution was injected and reacted for 3 hours. Next, the temperature was raised to 64 占 폚, and the pressure was reduced to the extent that the reflux of water occurred. 48 parts of a 49% aqueous solution of sodium hydroxide was added dropwise over 3 hours, and water and epichlorohydrin, , Epichlorohydrin was returned to the reaction vessel, and water was removed from the system and reacted. After the completion of the reaction, the temperature was raised to 70 캜 to perform dehydration, and the temperature was raised to 135 캜 to recover the remaining epichlorohydrin. The pressure was returned to normal pressure, and 204 parts of methyl isobutyl ketone (MIBK) was added and dissolved. 127 parts of ion-exchanged water was added, and the mixture was stirred to remove the by-produced salt dissolved in water. Next, 2.9 parts of a 49% sodium hydroxide aqueous solution was injected, and the mixture was stirred at 80 캜 for 90 minutes for purification. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain an epoxy resin (c4) in which X ^{1 in} the formula (1) was a 4-methylcyclohexylidene group, R ¹ was H, and n was 0.05. The obtained epoxy resin (c4) had an epoxy equivalent of 206.

Subsequently, 100 parts of the obtained epoxy resin (c4) and 0.12 part of tetramethylammonium iodide were injected into the same apparatus as in Synthesis Example 1, and the temperature was elevated while nitrogen gas was supplied, and the temperature was maintained at 120 占 폚 for 30 minutes . Next, 12.2 parts of diphenylmethane diisocyanate was added dropwise over 3 hours while being heated to 60 占 폚 while maintaining the reaction temperature at 130 占 폚 to 140 占 폚. After completion of the dropwise addition, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (Resin 4). The obtained resin 4 had a modification ratio (Rox) of 0.2, an epoxy equivalent of 290, and a softening point of 80 占 폚.

Synthesis Example 5

86.5 parts of 4,4'-cyclohexylidenebisphenol, 358 parts of epichlorohydrin and 4 parts of ion-exchanged water were charged into the same apparatus as in Synthesis Example 1, and the temperature was raised to 50 占 폚 with stirring. After uniformly dissolving, 5.3 parts of a 49% sodium hydroxide aqueous solution was injected and the reaction was carried out for 3 hours. Subsequently, the temperature was raised to 64 占 폚, and the pressure was reduced to the extent that the reflux of water occurred. 48 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours, and water and epichlorohydrin , Epichlorohydrin was returned to the reaction vessel, and water was removed from the system and reacted. After the completion of the reaction, the temperature was raised to 70 캜 to perform dehydration, and the temperature was raised to 135 캜 to recover the remaining epichlorohydrin. The pressure was returned to normal pressure, and 204 parts of MIBK was added and dissolved. 127 parts of ion-exchanged water was added, and the mixture was stirred to remove the by-produced salt dissolved in water. Next, 2.9 parts of a 49% sodium hydroxide aqueous solution was injected, and the mixture was reacted at 80 DEG C for 90 minutes with stirring to carry out a purification reaction. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain an epoxy resin (c5). The epoxy resin (c5) is an epoxy resin in which X ^{1 in} the formula (1) is a 4-cyclohexylidene group, R ¹ is H and n is 0.06, and the epoxy equivalent is 200.

Subsequently, 100 parts of the obtained epoxy resin (c5) and 0.11 part of tetramethylammonium iodide were introduced into the same apparatus as in Synthesis Example 1, and the temperature was elevated while nitrogen gas was supplied, and the temperature was maintained at 120 占 폚 for 30 minutes . Next, 12.5 parts of diphenylmethane diisocyanate was added dropwise over 3 hours while being heated to 60 占 폚 while maintaining the reaction temperature at 130 占 폚 to 140 占 폚. After completion of the dropwise addition, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (resin H1). The obtained resin H1 had a modification ratio (Rox) of 0.2, an epoxy equivalent of 285, and a softening point of 85 占 폚.

Synthesis Example 6

105 parts of phenol novolak (hydroxyl equivalent weight 105, softening point 130 캜) and 0.1 part of p-toluenesulfonic acid were charged in the same apparatus as in Synthesis Example 1 and the temperature was raised to 150 캜. While maintaining the same temperature, 94 parts of styrene was added dropwise over 3 hours, and stirring was further continued at the same temperature for 1 hour. Thereafter, 500 parts of MIBK was added, the contents were dissolved, and the pieces were washed 5 times at 80 캜. Subsequently, the MIBK was distilled off under reduced pressure to obtain a styrene-modified novolak phenol compound (APN-A). The obtained APN-A had a phenolic hydroxyl group equivalent of 199 and a softening point of 110 ° C. In the above formula (3), the average substitution number of 1-phenylethyl group per one A ¹ is 0.9.

Synthesis Example 7

105 parts of phenol novolac (phenolic hydroxyl group equivalent 105, softening point 67 캜) and 0.13 part of p-toluenesulfonic acid were charged in the same apparatus as in Synthesis Example 1, and the temperature was raised to 150 캜. While maintaining the same temperature, 156 parts of styrene was added dropwise over 3 hours, and stirring was further continued at the same temperature for 1 hour. Thereafter, the same treatment as in Synthesis Example 6 was carried out to obtain a styrene-modified novolak phenol compound (APN-B). The resulting APN-B had a phenolic hydroxyl group equivalent of 261 and a softening point of 75 캜. The average substitution number of 1-phenylethyl group ^per A ¹ is 1.5.

Synthesis Example 8

210 parts of 1-naphthol aralkyl resin (SN-475, phenolic hydroxyl equivalent equivalent 210, softening point: 77 占 폚) and 0.18 part of p-toluenesulfonic acid were charged in the same apparatus as in Synthesis Example 1 to obtain 150 Lt; 0 > C. While maintaining the same temperature, 135 parts of styrene was added dropwise over 3 hours, and stirring was further continued at the same temperature for 1 hour. Thereafter, the same treatment as in Synthesis Example 6 was carried out to obtain a styrene-modified novolak phenol compound (APN-C). The obtained APN-C had a phenolic hydroxyl group equivalent of 345 and a softening point of 88 캜. The average substitution number of 1-phenylethyl group ^per A ¹ is 1.3.

Synthesis Example 9

Into the same apparatus as in Synthesis Example 1, 500 parts of phenol and 19 parts of boron trifluoride ether complex were charged, and the temperature was raised to 120 占 폚. 176 parts of dicyclopentadiene was added dropwise over 6 hours while maintaining the same temperature, and the reaction was further carried out at 130 占 폚 for 4 hours. Thereafter, neutralization was carried out and phenol recovery was carried out. Further, 500 parts of MIBK was added, the contents were dissolved, and the pieces were rinsed 4 times at 80 캜. Subsequently, MIBK was distilled off under reduced pressure to obtain a dicyclopentadiene / phenol cocondensation resin.

Subsequently, 196 parts of the obtained dicyclopentadiene / phenol cocondensation resin and 0.11 part of p-toluenesulfonic acid were introduced into the same apparatus as in Synthesis Example 1, and the temperature was raised to 150 占 폚. While maintaining the same temperature, 31 parts of styrene was added dropwise over 3 hours, and stirring was further continued at the same temperature for 1 hour. Thereafter, the same treatment as in Synthesis Example 6 was carried out to obtain a substituent-containing novolak phenol compound (APN-D). The resulting APN-D had a phenolic hydroxyl group equivalent of 228 and a softening point of 122 캜. The average substitution number of 1-phenylethyl group ^per A ¹ is 0.3.

Synthesis Example 10

Into the same apparatus as in Synthesis Example 1, 500 parts of phenol and 9.5 parts of boron trifluoride ether complex were charged and the temperature was raised to 120 占 폚. While maintaining the same temperature, 88 parts of dicyclopentadiene was added dropwise over 6 hours, and the reaction was further carried out at 130 占 폚 for 4 hours. Thereafter, neutralization was carried out and phenol recovery was carried out. Further, 300 parts of MIBK was added, the contents were dissolved, and the pieces were rinsed four times at 80 캜. Subsequently, MIBK was distilled off under reduced pressure to obtain a dicyclopentadiene / phenol cocondensation resin.

Then, 178 parts of the obtained dicyclopentadiene / phenol cocondensation resin and 0.11 part of p-toluenesulfonic acid were injected into the same apparatus as in Synthesis Example 1, and the temperature was raised to 150 캜. While maintaining the same temperature, 32 parts of benzyl alcohol was added dropwise over 3 hours, and further stirring was continued at the same temperature for 1 hour. Thereafter, the same treatment as in Synthesis Example 6 was carried out to obtain a substituent-containing novolak phenol compound (APN-E). The resulting APN-E had a phenolic hydroxyl group equivalent of 205 and a softening point of 90 캜. The average substitution number of the benzyl group for one A ¹ was 0.3.

The abbreviations used in Examples and Comparative Examples are as follows.

(Epoxy resin)

(1) An epoxy resin containing an oxazolidone ring (a)

 Resins 1 to 4: The epoxy resin obtained in Synthesis Examples 1 to 4

(2) Other epoxy resins

 Resin H1: The epoxy resin obtained in Synthesis Example 5

 TX-1468: Tactics

 YDPN-638: phenol novolak type epoxy resin (Epototo YDPN-638, epoxy equivalent 176, manufactured by Shinnitetsu Sumikin Chemical Co., Ltd.)

 KDCP-130: dicyclopentadiene type epoxy resin (KDCP-130, epoxy equivalent: 254, manufactured by Kukdo Chemical Co., Ltd.)

(Hardener)

(1) Bisphenol compound (b1)

 BisP-TMC: 4,4 '- (3,3,5-trimethylcyclohexylidene) bisphenol (BisP-TMC, manufactured by Honshu Chemical Industry Co., Ltd., phenolic hydroxyl equivalent 155)

 BisP-MC: 4,4 '- (4-methylcyclohexylidene) diphenol (reagent, phenolic hydroxyl equivalent)

(2) The novolak phenol compound (b2)

 APN-A to E: The novolac phenol compound obtained in Synthesis Examples 6 to 10

(3) Other curing agents

 PN: phenol novolak resin (manufactured by Showa Denko K.K., Shonol BRG-557, phenolic hydroxyl equivalent 105, softening point 80 캜)

 Bis-Z: 4,4'-cyclohexylidenebisphenol (bis-Z, manufactured by Honshu Chemical Industry Co., Ltd., phenolic hydroxyl equivalent 134)

 DCPD: dicyclopentadiene phenol compound (GDP9140, manufactured by Kuniyou Chemical Co., Ltd., phenolic hydroxyl group equivalent: 196, softening point: 130 占 폚)

(Hardening accelerator)

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

(Flame retardant)

 SPE-100: phosphazene-based flame retardant (SPE-100 manufactured by Otsuka Chemical Co., Ltd., phosphorus content: 13%)

Example 1

100 parts of Resin 1 as an epoxy resin, 29.0 parts of BisP-TMC as a curing agent, 29.0 parts of APN-A and 0.2 parts of 2E4MZ as a curing accelerator were blended and mixed with MEK, propylene glycol monomethyl ether, N, N-dimethylformamide To obtain an epoxy resin composition varnish.

The obtained epoxy resin composition varnish was impregnated with glass cloth (ISO 7628 type, thickness 0.16 mm). The impregnated glass cloth was dried in a hot air circulating oven at 150 캜 to obtain a prepreg. 8 prepregs obtained above, and copper foils (3EC-III, thickness: 35 탆, manufactured by Mitsui Mining & Mining Co., Ltd.) were laminated on the upper and lower sides and vacuum press at 2 MPa was carried out at 130 캜 x 15 minutes + 190 캜 x 80 minutes To obtain a laminate having a thickness of 1.6 mm. The results of the glass transition temperature, copper foil peel strength and interlaminar adhesion of the laminate are shown in Table 1.

The obtained prepreg was loosened and sieved to prepare a prepreg powder in the amount of 100 mesh passes. The prepreg powder was placed in a mold made of a fluororesin and subjected to a vacuum press at 2 MPa under the condition of 130 占 폚 for 15 minutes + 190 占 폚 for 80 minutes to prepare a test piece of 50 mm in width and 2 mm in thickness ≪ / RTI > Table 1 shows the relative dielectric constant and dielectric tangent of the test pieces.

Examples 2 to 8

(Parts) shown in Table 1, and the same apparatus as in Example 1 was used and the same operation was carried out to obtain a laminate and a test piece. The same tests as in Example 1 were carried out, and the results are shown in Table 1. In the table, "b1 / b2 (equivalent ratio)" represents an equivalence ratio (molar ratio) of the bisphenol compound (b1) to the novolak phenol compound (b2). In all of the examples and comparative examples, the equivalent ratio (molar ratio) of the epoxy resin (A) to the curing agent (B) was 1.0.

Comparative Examples 1 to 7

(Parts) shown in Table 2, and the same apparatus as in Example 1 was used to carry out the same operation to obtain a laminate and a test piece. The same test as in Example 1 was carried out, and the results are shown in Table 2.

Examples 9 to 12 and Comparative Examples 8 to 10

(Parts) shown in Table 3, and the same apparatus as in Example 1 was used and the same operation was performed to obtain a laminate and a test piece. The same tests as in Example 1 were carried out, and the results are shown in Table 3.

Examples 13 to 16 and Comparative Example 11

(Parts) shown in Table 4, and the same apparatus as in Example 1 was used and the same operation was carried out to obtain a laminate and a test piece. The flame retardant was added in such an amount that the phosphorus content of the epoxy resin composition became 2.5%. The same tests as in Example 1 were carried out, and the results are shown in Table 4. [ The test pieces for flame retardancy measurement were produced by etching both surfaces of the laminate, and the test pieces were subjected to a flame retardance test. The results are shown in Table 4.

INDUSTRIAL APPLICABILITY The epoxy resin composition and the cured product of the present invention are excellent in heat resistance, adhesiveness and dielectric properties and can be used as an epoxy resin composition for applications such as epoxy resin cured products, prepregs and laminated plates. In addition, the epoxy resin composition and the cured product thereof further containing a flame retardant are excellent in flame retardance, heat resistance, adhesiveness, and dielectric properties, and can be suitably used for an epoxy resin composition .

Claims (6)

1. An epoxy resin composition comprising an epoxy resin (A) and a curing agent (B), wherein the epoxy resin (A) comprises an epoxy resin (c) represented by the following formula (1) and an oxazolidone ring- An epoxy resin composition comprising a resin (a) and a curing agent (B) containing a bisphenol compound (b1) represented by the following formula (2) and a novolac phenol compound (b2) represented by the following formula (3) .
[Chemical Formula 1]

(Wherein X ¹ represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one hydrocarbon group of 1 to 20 carbon atoms as a substituent, R ¹ each independently represents a hydrogen atom, a halogen atom, A halogenated hydrocarbon group or a hydrocarbon group of 1 to 20 carbon atoms which may have a hetero atom, G represents a glycidyl group, n represents a repeating number, and an average value is 0 to 5.)
(2)

(Wherein X ² represents a cycloalkylidene group having 5 to 8 ring atoms and having at least one hydrocarbon group of 1 to 20 carbon atoms as a substituent, R ² is independently a hydrogen atom, a halogen atom, A halogenated hydrocarbon group, or a hydrocarbon group of 1 to 20 carbon atoms which may have a hetero atom.
(3)

(Wherein A ¹ each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and the aromatic ring group may have a hydrocarbon group having 1 to 49 carbon atoms, which may have a heteroatom, And has an average of from 0.1 to 2.5 substituents selected from an aryl group having 6 to 48 carbon atoms, an aryloxy group having 6 to 48 carbon atoms, an aralkyl group having 7 to 49 carbon atoms, and an aralkyloxy group having 7 to 49 carbon atoms.
T represents a divalent aliphatic cyclic hydrocarbon group or a divalent bridging group represented by the following formula (3a) or (3b). k represents 1 or 2; m represents the number of repeats, and the average value is 1.5 or more.)
[Chemical Formula 4]

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom, R ⁵ and R ⁶ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms A ² represents an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups may have a hydrocarbon group of 1 to 20 carbon atoms which may have a hetero atom as a substituent. The method according to claim 1,
Wherein the mass ratio of the bisphenol compound (b1) to the novolac phenol compound (b2) is in the range of 5/95 to 95/5. 3. The method according to claim 1 or 2,
Wherein the bisphenol compound (b1) is 4,4 '- (3,3,5-trimethylcyclohexylidene) bisphenol or 4,4' - (3,3,5,5-tetramethylcyclohexylidene) bisphenol Epoxy resin composition. 4. The method according to any one of claims 1 to 3,
Wherein the novolak phenol compound (b2) is a phenol compound represented by the following formula (4).
[Chemical Formula 5]

(Wherein, R ⁷ are each independently represents a hydrocarbon group of a carbon number of 1 ~ 6, R ⁸ is a substituent group represented by the following formula (4a). P is 0.1 to 2.5 as an average, q is a number from 0-2, p + q is an average value of 0.1 to 3. m is the agreement with m in equation (3).)
[Chemical Formula 6]

(Wherein R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) 5. The method according to any one of claims 1 to 4,
Wherein the active hydrogen group of the curing agent (B) relative to 1 mole of the epoxy group of the epoxy resin (A) is 0.2 to 1.5 moles. An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 5.