TW201809130A - 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). X1 and X2 are a cycloalkylidene group with 5 to 8 ring atoms which has a hydrocarbon group as a substituent, A1 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 hardened material thereof

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

Due to the remarkable progress of electrical and electronic equipment, especially the large-capacity and high-speed processing of data by communication equipment, dielectric materials such as printed wiring boards and sealing materials used in these devices have low dielectric constants and low dielectric loss tangents. Demands for features are increasing. In addition, the wiring of the metal foil ensures the adhesive force by roughening the adhesive surface. However, for high-speed processing, the problem of suppressing the roughening and maintaining the adhesive force also obviously exists.

Infrastructure equipment such as portable devices or base stations that maintain the use of printed wiring boards is one of the uses of printed wiring boards. With the rapid increase in the amount of information in recent years, high functional requirements have been required. In portable devices, miniaturization is used to achieve high-level multilayers or fine wiring. Materials that require a lower dielectric constant in order to make substrates thinner, and fine-wiring reduces the bonding surface. Highly adhesive material. In the base station-oriented substrate, in order to suppress attenuation of a high-frequency signal, a material having a lower dielectric loss tangent is required.

The characteristics such as low dielectric constant, low dielectric loss tangent, and high adhesive force are largely derived from the structure of an epoxy resin and a hardener as a base resin of a printed wiring board.

It is known that a hydroxyl group generated when the epoxy resin composition is cured deteriorates the dielectric constant. As one of the designs with a reduced number of hydroxyl groups, Patent Document 1 discloses an oxazolidone ring-containing epoxy resin that generates an oxazolidone ring by the reaction of an epoxy resin and an isocyanate. Examples of the raw material epoxy resin include glycidylated compounds such as diphenols such as bisphenol A, tris (glycidyloxyphenyl) alkanes, and glycidized compounds such as aminophenol. Or a glycidylated compound such as phenol novolac. However, none of the disclosed epoxy resins satisfies the requirements for high-functionality dielectric properties in recent years, and the adhesiveness is also insufficient.

As a method for improving the dielectric properties of epoxy resins, as shown by Clausius-Mossotti's formula, it is effective to reduce the molar polarizability and increase the molar volume . As a hardener to which this effect of increasing the Mohr volume is applied, Patent Document 2 discloses a dicyclopentadiene phenol resin. Patent Document 3 discloses cycloalkylene bisphenols containing a substituent such as 4,4 ′-(3,3,5-trimethylcyclohexylene) bisphenol, but there is no disclosure about dielectric properties.

On the other hand, Patent Documents 4 and 5 disclose that aromatic modified phenol novolacs are used as hardeners. Although they have excellent heat resistance, dielectric properties, and the like, there is a problem that the adhesive force is easily insufficient. [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 5-43655 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 2015-535865 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 2-229181 [Patent Literature 4] ] Japanese Patent Laid-Open No. 2010-235819 [Patent Document 5] Japanese Patent Laid-Open No. 2012-57079

[Problems to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to provide properties having excellent low dielectric properties, high heat resistance, and high adhesion, and useful in applications such as lamination, molding, casting, and adhesion. Epoxy resin composition and its hardened product. In addition, even when a flame retardant is blended, an epoxy resin composition and a cured product thereof having good flame retardancy without deteriorating characteristics such as dielectric properties, heat resistance, and adhesiveness are provided. [Technical means to solve the problem]

In order to solve the above problems, the present inventors made earnest research on a low dielectric constant and low dielectric loss tangent material. As a result, they found that an oxazolidinone containing an epoxy resin having a specific structure and an isocyanate compound are reacted. Oxazolidone ring epoxy resin, and epoxy resin composition using a combination of a specific bisphenol compound and a specific novolac phenol compound hardener simultaneously achieve low dielectric constant and low dielectric loss tangent With a high glass transition temperature, and thus good adhesion, the present invention has been completed. It has also been found that even when used in combination with a flame retardant, excellent flame retardance is exhibited without deteriorating characteristics such as dielectric properties, heat resistance, and adhesiveness.

That is, this invention is an epoxy resin composition containing an epoxy resin (A) and a hardening | curing agent (B), The said epoxy resin composition is characterized in that the epoxy resin (A) contains the following formula ( 1) The oxazolidone ring-containing epoxy resin (a) obtained from the epoxy resin (c) and the isocyanate compound (d) represented by the epoxy resin (c), and the hardener (B) contains the bis represented by the following formula (2) The phenol compound (b1) and the novolac phenol compound (b2) represented by the following formula (3).

[Chemical 1] In the formula, X ¹ represents a cycloalkylidene having 5 to 8 ring members having at least one hydrocarbon group having 1 to 20 carbon atoms as a substituent. R ¹ each 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. G represents glycidyl. n represents the number of repetitions, and the average value is 0 to 5.

[Chemical 2] In the formula, X ² represents a cycloalkylene group having 5 to 8 ring members having at least one hydrocarbon group having 1 to 20 carbon atoms as a substituent. R ² each 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.

[Chemical 3] In the formula, A ¹ each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring. These aromatic ring groups may have a hydrocarbon group having 1 to 49 carbon atoms which may have a hetero atom as a substituent. Group having, on average, 0.1 to 2.5 aryl groups selected from 6 to 48 carbon atoms, aryloxy groups 6 to 48 carbon atoms, aralkyl groups 7 to 49 carbon atoms, and aralkoxy groups 7 to 49 carbon atoms A substituent in a radical. T represents any of a divalent aliphatic cyclic hydrocarbon group or a divalent crosslinking group represented by the following formula (3a) or the following formula (3b). k represents 1 or 2. m represents the number of repetitions, and the average value is 1.5 or more. [Chemical 4] In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have 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 having 1 to 20 carbon atoms which may have a hetero atom as a substituent.

In the said epoxy resin composition, the preferable aspect of this invention is satisfying any one or more of the following. 1) The mass ratio of the bisphenol compound (b1) to the novolac phenol compound (b2) is in the range of 5/95 to 95/5, 2) The bisphenol compound (b1) is 4,4 '-(3,3,5 -Trimethylcyclohexylene) bisphenol or 4,4 '-(3,3,5,5-tetramethylcyclohexylene) bisphenol, 3) novolac phenol compound (b2) is the following formula (4 The phenol compound represented by), or 4) The active hydrogen group of the hardener (B) is 0.2 mol to 1.5 mol with respect to 1 mol of the epoxy group of the epoxy resin (A).

[Chemical 5] In the formula, R ⁷ each 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 0.1 to 3 as an average value, and m has the same meaning as m in formula (3). [Chemical 6] In the formula, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

The present invention is an epoxy resin cured product obtained by curing the epoxy resin composition. [Effect of the invention]

The epoxy resin composition of the present invention provides a hardened product that maintains good adhesion and has a high glass transition temperature. Furthermore, the cured product of the present invention is also excellent in dielectric characteristics, and exhibits good characteristics in electronic material applications that require a low dielectric constant and a low dielectric loss tangent.

Hereinafter, embodiments of the present invention will be described in detail. The epoxy resin composition of this invention contains an epoxy resin (A) and a hardening | curing agent (B). The epoxy resin (A) contains an oxazolidone ring-containing epoxy resin (a) as an essential component. The hardener (B) contains a bisphenol compound (b1) and a novolac phenol compound (b2) as essential components.

The epoxy equivalent (g / eq.) Of the oxazolidone ring-containing epoxy resin (a) is preferably 200 to 1,000, more preferably 220 to 700, still more preferably 230 to 500, and particularly preferably 250 to 400. If the epoxy equivalent is low, there is a concern that the content of the oxazolidone ring becomes small and the hydroxyl group concentration in the cured product becomes high, so that the dielectric constant becomes high. In addition, if the epoxy equivalent is high, there is a concern that the content of the oxazolidone ring needs to be increased more than necessary, and adverse effects such as deterioration of solvent solubility or increase in resin viscosity due to the effect of improving the dielectric properties are increased. In addition, there is a concern that the crosslinked density of the hardened material becomes low, so that the elastic modulus decreases at the temperature of reflow soldering, and the like, which poses a problem in use.

The softening point of the oxazolidone ring-containing epoxy resin (a) when used in a prepreg or a film material is preferably 50 ° C to 150 ° C, more preferably 60 ° C to 135 ° C, and furthermore It is preferably 70 ° C to 110 ° C. If the softening point is low, there is a concern that when the resin varnish is impregnated in a glass cloth and then heated and dried in an oven, the viscosity of the resin is low, so that the amount of resin attached is reduced. If the softening point is high, there is a concern that the viscosity of the resin becomes high, the impregnation in the prepreg deteriorates, or the solubility of the solvent deteriorates, or the diluted solvent does not volatilize and remains in the resin during heating and drying. When a laminated board is produced, voids and the like are generated, which is a problem in use.

The oxazolidone ring-containing epoxy resin (a) can be advantageously obtained by a method for producing an oxazolidone ring-containing epoxy resin described later, but usually, an oxazolidone ring-containing Epoxy. Here, by-products and the like can be interpreted as including unreacted substances. The oxazolidone ring-containing epoxy resin (a) may be a reaction product containing such a by-product.

The oxazolidone ring-containing epoxy resin (a) is obtained by a reaction between the epoxy resin (c) represented by the formula (1) and an isocyanate compound (d). In this reaction, an epoxy group and an isocyanate group react to form an oxazolidone ring. Typically, when a bifunctional epoxy resin and an isocyanate compound are used together, they will have a structural unit represented by the following formula. -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, and Ox ¹ is an oxazolidine Ketone ring, Ic ¹ is a residue obtained by removing an isocyanate group from an isocyanate.

In formula (1), R ¹ each 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 hetero atom-containing hydrocarbon group in which a portion of the carbon constituting the hydrocarbon group or a carbon constituting the hydrocarbon group is a hetero atom. A heteroatom-containing hydrocarbon group is one in which a part of carbon constituting a hydrocarbon chain or a hydrocarbon ring is a heteroatom, and in the case of a hydrocarbon chain, it may be located at the middle or at the end. Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom, and an oxygen atom is preferred. In the case where the hetero atom is an oxygen atom, which is located at the terminal, and the hydrocarbon group is an alkyl group, an aryl group, or an aralkyl group, it may be an alkoxy group, an aryloxy group, or an aralkoxy group. In addition, the hetero atom may be located in a hydroxy-like substituent.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a halogenated alkyl group having 1 to 20 carbon atoms, and preferably 1 to 6 carbon atoms.

The hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom may be linear, branched, or cyclic, and is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, Or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a ring having 5 to 8 carbon atoms Alkoxy, aryl having 6 to 14 carbons, aryloxy having 6 to 14 carbons, aralkyl having 7 to 15 carbons, or aralkoxy having 7 to 15 carbons. These may make a part of carbon a hetero atom. Examples of the alkyl or alkoxy group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, methoxy, ethoxy, Propoxy, isopropoxy, n-butoxy, tert-butoxy, hexyloxy, etc. Examples of the cycloalkyl or cycloalkoxy group having 5 to 8 carbon atoms include cyclohexyl, cyclohexyloxy, etc. Examples of the aryl group or aryloxy group having 6 to 14 carbon atoms include phenyl, tolyl, o-xylyl, naphthyl, dihydroindenyl, phenoxy, and naphthyloxy, and the carbon number is 7 Examples of aralkyl or aralkyloxy groups of 15 to benzyl, phenethyl, 1-phenylethyl, naphthylmethyl, anthrylmethyl, benzyloxy, naphthylmethoxy, and anthracene Butylmethoxy and the like are not limited to these, and may be the same or different.

When flame retardance is required, a halogen atom or a halogenated hydrocarbon group having 1 to 20 carbon atoms is preferably used 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 brominated methyl group and the like. However, in the case of the non-halogen flame-retardant epoxy resin composition mentioned later, the substituent which has such a halogen atom is not included.

From the viewpoints of availability and hardened properties, 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. The substitution position of R ^{1 is} any of ortho, para and meta positions with respect to the carbon atom bonded to X ¹ , preferably ortho or para, and more preferably ortho.

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

From the viewpoint of dielectric properties, the hydrocarbon group having 1 to 20 carbon atoms as a substituent is preferably a structure having a large molecular weight, and is preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and carbon. An aryl group having 6 to 14 or an aralkyl group having 7 to 15 carbons. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, and hexyl. As the cycloalkyl group having 5 to 8 carbon atoms, Examples include cyclohexyl and the like. Examples of aryl having 6 to 14 carbon atoms include phenyl, tolyl, o-xylyl, and naphthyl. Examples of aralkyl having 7 to 15 carbon atoms include benzyl. , Phenethyl, 1-phenylethyl, and the like are not limited to these, and when there are a plurality of them, they may be the same or different. From the viewpoint of ease of acquisition and physical properties of the cured product, preferred substituents are alkyl groups having 1 to 3 carbon atoms or phenyl groups, and more preferably methyl groups.

In addition, the cycloalkylene group is a 1,1-cycloalkylene group, and the substituent group is caused by a steric repulsive effect that interacts with two benzene rings or substituent groups bonded to the carbon at the 1 position of the cycloalkylene group. Restricting the mobility of the naphthenic ring results in improved dielectric properties and improved heat resistance. This substitution position may be bonded to any position as long as it can restrict mobility, but it is preferably bonded to a carbon atom close to the 1-position of the cycloalkylene group. Preferred substituents have a carbon atom at the 2- or 5-position in the cyclopentane ring. In the cyclohexane ring, it is a carbon atom at the 2-, 3-, 5-, or 6-position, and more preferably a 2- or 6-position carbon atom. In the cycloheptane ring, it is a carbon atom at the 2-, 3-, 6-, or 7-position, and more preferably a 2- or 7-position carbon atom. In the cyclooctane ring, it is a carbon atom at the 2-, 3-, 4-, 6-, 7-, or 8-position, more preferably a 2-, 3-, 7-, or 8-position carbon atom, and further preferably 2 Or 8 carbon atoms. Among them, due to the influence of steric hindrance with the adjacent benzene ring, it may be difficult to substitute the carbon atom closest to the 1st position. In this case, the substituent is suitable to be bonded to the second nearest carbon atom. For example, in a cyclohexane ring, the carbon atom at the 2 or 6 position is closest to the 1 position, but in the case where it is difficult to replace due to steric hindrance, the substituent may be bonded to the 3 or 5 position nearest to .

In addition, the number of substituents requires at least one for the reasons described above, but from the viewpoint of physical properties such as heat resistance of the cured product, it is preferably three or more, and more preferably three.

In the formula (1), n is a repeating number, and an average value (number average) thereof is 0 to 5, preferably 0 to 3, more preferably 0 to 1, still more preferably 0 to 0.5, and most preferably 0. The repeating number may be a single compound having any integer of 0 to 5, or a mixture of a plurality of integers having n being 0 to 5.

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 equivalent (g / eq.) Is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. The alcoholic hydroxyl group reacts with an isocyanate to generate a urethane bond, which lowers the glass transition point of the cured product. Therefore, the alcoholic hydroxyl equivalent is small, which is not preferable. Moreover, since the hydroxyl group concentration in a hardened | cured material increases, the dielectric constant of a hardened | cured material becomes high, and it is also unpreferable.

Examples of the epoxy resin (c) include epoxy resins obtained from a cycloalkylene-containing bisphenol compound and epihalohydrin represented by the formula (2). Examples include 4,4 '-(2-methylcyclohexylene) bisphenol glycidyl ether, 4,4'-(3-methylcyclohexylene) bisphenol glycidyl ether, 4,4 '-( 4-methylcyclohexylene) bisphenol glycidyl ether, 4,4 '-(3,3,5-trimethylcyclohexylene) bisphenol glycidyl ether, 4,4'-(3,3,5 -Trimethylcyclohexylene) -bis-dimethylphenol glycidyl ether, 4,4 '-(3,3,5-trimethylcyclohexylene) -bis-tert-butylphenol glycidyl ether, etc., However, it is not limited to these, and they may be used alone or in combination of two or more.

In terms of ease of acquisition and good physical properties of the cured product, the epoxy resin (c) is preferably composed of 4,4 '-(3,3,5-trimethylcyclohexylene) bisphenol and epihalohydrin. The obtained epoxy resin (c1) represented by following formula (5). In addition, n in formula (5) has the same meaning as n in formula (1). [Chemical 7]

When the oxazolidone ring-containing epoxy resin (a) is produced, a desired oxazolidone ring-containing epoxy resin can be obtained by reacting the epoxy resin (c) with an isocyanate compound (d). As long as the isocyanate compound (d) is an isocyanate compound having an average of 1.8 or more isocyanate groups (-N = C = O) in one molecule, that is, a polyfunctional isocyanate compound that is substantially difunctional or more, known and conventional ones can be used. Of isocyanate compounds. Although a monofunctional isocyanate compound may be contained in a small amount, it becomes a terminal group, and therefore it is effective for the purpose of reducing the degree of polymerization, but the degree of polymerization is not high.

Specific examples include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,5-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 2,4'-diphenyl Methane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethylxylene diisocyanate, 1,4-naphthalene diyl diisocyanate, 1,5 -Naphthalene diyl diisocyanate, 2,6-naphthalene diyl diisocyanate, 2,7-naphthalene diyl diisocyanate, naphthalene-1,4-diyl bis (methylene) diisocyanate, naphthalene-1,5- Diyl bis (methylene) diisocyanate, m-phenylene diisocyanate, terephthalic diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate , 2,3'-dimethoxybiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4, 4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate, diphenylsulfite-4,4'-diisocyanate, diphenylfluorene-4,4 '-Diisocyanate, bicyclic [2.2.1] heptane-2,5-diylbismethylene diisocyanate, bis [2.2.1] heptane-2,6-diylbismethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebiscyclohexyl diisocyanate, lysine diisocyanate, 1,1 -Bis (isocyanatemethyl) cyclohexane, 1,2-bis (isocyanatemethyl) cyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) ring Hexane, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4-methyl-1,3-cyclohexylene diisocyanate, 2-methyl-1,3-cyclohexylene Diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3, 5-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, methane diisocyanate, ethane -1,2-diisocyanate, propane-1,3-diisocyanate, butane-1,1-diisocyanate, butane-1,2-diisocyanate, butane-1,4-diisocyanate, 2-butane Ene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentyl -1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane-1, Difunctional isocyanate compounds such as 8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diphenylsilane diisocyanate, or triphenylmethane Isocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, dicycloheptane triisocyanate, tris (isocyanatephenyl) thiophosphate , Lysine triisocyanate, undecane triisocyanate, tris (4-phenylisocyanate thiophosphate) -3,3 ', 4,4'-diphenylmethane tetraisocyanate, polymethylene polybenzene Polyfunctional isocyanate compounds such as diisocyanates, or polymers such as dimers or trimers of the isocyanate compounds, or block isocyanates that are masked with block agents such as alcohols or phenols, or biscarbamates Compounds and the like are not limited to these. These isocyanate compounds may be used alone or in combination of two or more kinds.

Among these isocyanate compounds, a difunctional isocyanate compound or a trifunctional isocyanate compound is preferable, and a difunctional isocyanate compound is more preferable. When there are many functional groups of an isocyanate compound, there exists a possibility that storage stability may fall, and when there are few functional groups of an isocyanate compound, there exists a possibility that heat resistance or dielectric characteristics may not improve. A further preferred isocyanate compound is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,5-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 2,4'-di Phenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethylxylene diisocyanate, 1,4-naphthalene diyl diisocyanate, 1, 5-naphthalenediyl diisocyanate, 2,6-naphthalenediyl diisocyanate, 2,7-naphthalenediyl diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, m-phenylene diisocyanate Isocyanate, terephthalic diisocyanate, cyclohexane-1,4-diyl diisocyanate, cyclohexane-1,3-diylbismethylene diisocyanate, cyclohexane-1,4-diylbismethylene Diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4,4'-methylene Dicyclohexyl diisocyanate, bicyclo [2.2.1] heptane-2,5-diylbismethylene diisocyanate, bicyclo [2.2.1] heptane-2,6-diylbismethylene diisocyanate, Isophorone Cyanate group consisting of one or more. Among these, a particularly preferred isocyanate compound (d) is selected from the group consisting of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,5-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, cyclohexane-1,3-diylbismethylene diisocyanate, cyclohexane-1,4-di One or more of the group consisting of a bismethylene diisocyanate and an isophorone diisocyanate.

The reaction between the epoxy resin (c) and the isocyanate compound (d) can be performed by a known method. The specific reaction methods are: (1) melting the epoxy resin (c), removing the moisture in the epoxy resin by using dry gas flushing or reducing the pressure in the system, and then adding the isocyanate compound (d) and A method of reacting with a catalyst; or (2) Premixing the epoxy resin (c) with the catalyst in advance, removing the moisture from the epoxy resin by using dry gas flushing or reducing the pressure in the system, and then adding an isocyanate compound (D) A method for performing the reaction and the like. The amount of water in the system at this time is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.05% by mass or less. In addition, in any method, if the resin has a high viscosity and it is difficult to stir, etc., a non-reactive solvent may be used if necessary. In this manner, 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 alcoholic hydroxyl group and an isocyanate group of the isocyanate compound (d) undergo an addition reaction to form a urethane bond. Except for the case where n in the formula (1) is 0, there are impurities added by the urethane bond. The oxazolidone ring-containing epoxy resin (a) used in the present invention includes not only the oxazolidone ring-containing epoxy resin, but also the unreacted raw material epoxy resin (c). In addition, an impurity that undergoes an addition reaction using a urethane bond may be included. Even if it is a mixture of these, it is contained in the oxazolidone ring containing epoxy resin (a) used by this invention.

The epoxy equivalent (No) of the oxazolidone ring-containing epoxy resin (a) can be predicted according to the following calculation formula according to the type of the raw material and the amount of the raw material. On the other hand, for the epoxy equivalent (a) containing the oxazolidone ring of the desired epoxy equivalent, the epoxy equivalent (Ne) of the epoxy resin (c) and the isocyanate group of the isocyanate compound (d) can be used. The equivalent weight (Ni) was calculated according to the following calculation formula, and the charged amounts of the epoxy resin (c) and the isocyanate compound (d) were determined. The unit of equivalent is g / eq., Unless otherwise specified, the same applies hereinafter.

[Number 1] Me: loading amount (g) of epoxy resin (c) Mi: loading amount (g) of isocyanate compound (d)

For example, when the epoxy equivalent of the epoxy resin (c) is 220 and the isocyanate group equivalent of the isocyanate compound (d) is 125, the epoxy equivalent of the epoxy resin (a) containing an oxazolidone ring The loading amount was about 500, and the isocyanate compound (d) was 30 parts by mass based on 100 parts by mass of the epoxy resin (c) according to the calculation formula.

From the viewpoints of suppression of high viscosity, securing of solvent solubility, or improvement of toughness, adhesiveness, and electrical properties, the oxazolidone ring-containing epoxy resin (a) used in the present invention is The azolidone ring modification rate is preferably 0.15 to 0.6, more preferably 0.2 to 0.5, and even more preferably 0.25 to 0.45. If the oxazolidone ring modification ratio is large, it becomes a macromolecule or becomes highly viscous, and there is a concern that the solubility of the solvent will decrease. In addition, if the oxazolidone ring modification rate is small, the rigid and high molecular interactions will have fewer oxazolidone rings, and the effect of improving the heat resistance or adhesion of the cured product will be insufficient. In many cases, the effect of improving electrical characteristics is insufficient. In addition, since the oxazolidone ring modification rate is substantially determined by the ratio of an epoxy group and an isocyanate group used, the oxazolidone ring modification rate is defined by the following formula in this specification.

Modification rate of oxazolidone ring = (isocyanate group mol) / (epoxy group mol)

For example, the oxazolidone ring-modified epoxy resin having an epoxy equivalent of about 500 has an oxazolidone ring modification ratio of 0.53.

Specific examples of the non-reactive solvent that can be used by the reaction between the epoxy resin (c) and the isocyanate compound (d) include hexane, heptane, octane, decane, dimethylbutane, Hydrocarbons such as pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Or ether, isopropyl ether, butyl ether, diisopentyl ether, methyl phenyl ether, ethyl phenyl ether, pentyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran, diethylene glycol di Ethers such as methyl ether, ethylene glycol diethyl ether, methyl ethyl carbitol, or methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, methyl acetate, ethyl acetate Ester, propyl acetate, butyl acetate, diethyl oxalate, etc., or N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc. Amidoamines, or lactones such as γ-butyrolactone, or fluorenes such as dimethylmethylene, or ureas such as tetramethylurea, or dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, chlorobenzene, o-dichlorobenzene Halogenated hydrocarbons, but are not limited to, non-reactive solvents which may be used alone, or two or more may be used in mixture. The usage-amount of these solvents is 1-900 mass parts with respect to 100 mass parts of epoxy resin (c), More preferably, it is 5-100 mass parts.

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

The reaction temperature is preferably 100 ° C to 250 ° C, more preferably 100 ° C to 200 ° C, and even more preferably 120 ° C to 160 ° C. If the reaction temperature is low, the formation of the oxazolidone ring cannot proceed sufficiently, and the isocyanurate ring is formed by the trimerization reaction of the isocyanate group. In addition, when the reaction temperature is high, a local high molecular weight is generated, and the generation of insoluble gel components increases. 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, the oxazolidone ring can be formed 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 after the addition of the isocyanate compound (d) is completed, more preferably 30 minutes to 8 hours, and still more preferably 1 hour to 5 hours. If the reaction time is short, there is a concern that a large amount of isocyanate groups remain in the product, and if the reaction time is long, there is a concern that productivity is significantly reduced.

The type of the catalyst used in the reaction is not particularly limited as long as it is a basic catalyst. Specific examples include lithium compounds such as lithium chloride and lithium butoxylate, boron trifluoride salts, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, and Quaternary ammonium salts such as butylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, dimethylaminoethanol, triethylamine, tributylamine, benzyldimethyl Tertiary amines such as trimethylamine, N-methylmorpholine, N, N'-dimethylpyrazine, 1,4-diethylpyrazine, triphenylphosphine, tris (2,6-dimethoxy Phosphines such as phosphine), pentyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium Phenylphosphonium iodide, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, tetrabutylphosphonium acetate · acetic acid complex, tetrabutylphosphonium acetate, Tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide and other phosphonium salts, a combination of triphenylantimony and iodine, 2-phenylimidazole, 2-methylimidazole, 2-ethyl -4-methylimidazole and other imidazoles, but not limited to these, these catalysts can be used alone or in combination the above. In addition, it can be divided and used several times.

Among these catalysts, quaternary ammonium salts, tertiary amines, phosphines, or phosphonium salts are preferred, and tetramethylammonium iodide is more preferred in terms of reactivity and selectivity of the reaction. In the case of a catalyst having a low reactivity, there is a concern that the reaction time becomes long and the productivity is lowered. In the case of a catalyst having a low selectivity of the reaction, there is a concern that an epoxy group may undergo polymerization reaction and the target physical properties may not be obtained.

The amount of the catalyst used is not particularly limited, and it is 0.0001 to 5 mass%, preferably 0.0005 to 1 mass%, and more preferably 0.0005 to 1 mass% with respect to the total mass of the epoxy resin (c) and the isocyanate compound (d). 0.001% by mass to 0.5% by mass, and more preferably 0.002% by mass to 0.2% by mass. If the amount of the catalyst is large, the self-polymerization reaction of the epoxy group proceeds depending on the case, and therefore the resin viscosity becomes high. In addition, it promotes the self-polymerization reaction of the isocyanate and suppresses the formation of the oxazolidone ring. Furthermore, there is a concern that it may remain as an impurity in the produced resin, and when used as a material for a laminated board or a sealing material in various applications, it may cause a reduction in insulation or moisture resistance.

The hardener (B) includes a bisphenol compound (b1) represented by the formula (2) and a novolac phenol compound (b2) represented by the formula (3). The mixing ratio (b1 / b2; mass ratio) of the bisphenol compound (b1) and the novolac phenol compound (b2) is preferably 5/95 to 95/5, more preferably 10/90 to 90 to 10, and even more preferably 20 / 80 to 80/20, and particularly preferably 30/70 to 70/30. If the epoxy resin (A) is only a mixture of an epoxy resin (a) containing an oxazolidone ring and a hardener (B) is only a mixture of a bisphenol compound (b1) and a novolac phenol compound (b2), the maximum value can be obtained. The effect of the present invention is exhibited to a limited extent. In addition, if the composition is contained in the epoxy resin composition, the content effect can be added compared to the case where it is not contained, and therefore, it can be added in a small amount.

The content of the oxazolidone ring-containing epoxy resin (a) in the epoxy resin (A) is preferably 5% to 100% by mass, more preferably 20% to 100% by mass, and even more preferably 50% by mass. It is 100% by mass, particularly preferably 70% by mass to 100% by mass, and most preferably 100% by mass. The content of the mixture of the bisphenol compound (b1) and the novolac phenol compound (b2) in the hardener (B) is preferably 5% to 100% by mass, more preferably 20% to 100% by mass, and still more preferably 50%. Mass% to 100% by mass, particularly preferably 70% to 100% by mass, and most preferably 100% by mass. When a reaction product containing a by-product or the like is used as the oxazolidone ring-containing epoxy resin (a), the content of the epoxy resin (a) containing the oxazolidone ring in the reaction product is significant. In some cases (for example, 20% by mass or less), the mass of the reaction product can be calculated as the mass of the oxazolidone ring-containing epoxy resin (a).

The bisphenol compound (b1) is represented by the formula (2). In formula (2), R ² each 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. These are the same as those described for R ¹ in formula (1). X ² is a cycloalkylene group having 5 to 8 ring members, and has at least one hydrocarbon group having 1 to 20 carbon atoms as a substituent. These are the same as those described in X ¹ in Formula (1).

The bisphenol compound (b1) can be obtained by reacting a corresponding cyclic aliphatic ketone with a phenol. Specific examples of the bisphenol compound (b1) include, but are not limited to, cycloalkylene-containing bisphenol compounds as shown below. In addition, the residue obtained by removing two hydroxyphenyl groups (in the case of having a substituent other than hydrogen) from the bisphenol compound described below is X ² , which is also preferably X ¹ . The substituent similarly substituted for the two hydroxyphenyl groups is R ² , which is also a preferred R ¹ .

[Chemical 8]

These exemplified cycloalkylene-containing bisphenol compounds can be produced, for example, by the method disclosed in Japanese Patent Laid-Open No. 4-282334 or Japanese Patent Laid-Open No. 2015-51935, or they can be used as commercially available products. Obtain, for example: BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisOCP-IPZ, BisP-nBZ, BisOEP-2HBP (the above are the trade names , Manufactured by Honshu Chemical Industry Co., Ltd.). Among these, 4,4 '-(3,3,5-trimethylcyclohexylene) bisphenol, 4,4'-(3, 3,5,5-tetramethylcyclohexylene) bisphenol, more preferably 4,4 '-(3,3,5-trimethylcyclohexylene) bisphenol.

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

In the formula (3), A ¹ each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring. These aromatic ring groups may have a hydrocarbon group having 1 to 49 carbon atoms which may have a hetero atom. As the substituent (R ²⁰ ), 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 aralkoxy group having 7 to 49 carbon atoms. One. The substituent (R ¹⁸ ) is preferably a group represented by the formula (4a) or a phenyl group, a naphthyl group, a dihydroindenyl group, a 2-phenylethyl group, a naphthylmethyl group, an anthrylmethyl group, and a phenoxy group. , Naphthyloxy, benzyloxy, and naphthylmethoxy, more preferably benzyl and 1-phenylethyl. By having a substituent (R ¹⁸ ), the physical properties of the cured product can be made good.

The aromatic ring group constituting A ¹ may have other substituents (R ¹⁷ ) in addition to the essential substituents (R ¹⁸ ). Here, the substituent (R ¹⁸ ) and the substituent (R ¹⁷ ) are understood as one kind of the 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 carbon number is different. The substituent (R ¹⁸ ) corresponds to R ⁸ in Formula (4), and the substituent (R ¹⁷ ) corresponds to R ⁷ in Formula (4), but R ⁷ and R ^{8 are} further limited as described later.

The introduction of these substituents (R ¹⁸ ) can be achieved by preparing phenols containing a substituent (R ¹⁸ ), such as phenylphenol, cumylphenol, styrenated phenol, benzylphenol, and phenoxyphenol, as raw materials. Obtained by novolacization. In this case, the number of substituents (R ¹⁸ ) of phenols containing a substituent (R ¹⁸ ) directly becomes the average of the number of substituents (R ¹⁸ ). In the case of adjusting the number of the substituent (R ^18), substituted phenols and long containing substituent group (R ¹⁸⁾ with phenols or unsubstituted phenols not containing substituent group (R ¹⁸⁾ substituent Just fine. In addition, by using an aralkylating agent with respect to the novolak phenol compound, a substituent (R ¹⁸ ) may be introduced. In this case, the molar amount of the aralkylating agent used for one aromatic ring of the novolac phenol compound is an average value of the number of substituents (R ¹⁸ ). It is preferably an aralkylating agent having an addition of 0.1 mol to 2.5 mol to one aromatic ring of the novolac phenol compound, more preferably 0.5 mol to 2.0 mol, and still more preferably 1.0 mol to 1.5 moles.

Examples of the aralkylating agent include a phenylmethanol compound, a phenylhalomethane compound, a naphthylmethanol compound, a naphthylhalomethane compound, and a styrene compound. Specific examples include benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, and p-ethylbenzyl. Methyl chloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl chloride, p-phenylbenzyl chloride, 5-chloromethylphosphonium, 2-naphthylmethyl chloride, 1-chloromethyl 2-naphthalene and its nuclear substituted isomers, α-methylbenzyl chloride, α, α-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 substituted isomers thereof, benzyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether P-methylbenzyl methyl ether and these nuclear substituted isomers, benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, Isopropylbenzyl alcohol, p-tert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthyl methanol and nuclear substituted isomers thereof, α-methylbenzyl alcohol, α, α-dimethyl Benzyl alcohol, styrene, o-methylstyrene, m-methylstyrene , P-methyl styrene, methyl styrene alpha], [beta] -methylstyrene. The styrene compound may contain a small amount of other reaction components (for example, components containing unsaturated bonds such as divinylbenzene, indene, coumarone, benzothiophene, indole, vinylnaphthalene, etc.). These can be used individually or in combination of 2 or more types. Among these, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and α-formaldehyde are preferred because they have excellent heat resistance and lower dielectric constant and dielectric loss tangent. Styrene, β-methylstyrene, benzyl chloride, benzyl bromide, or benzyl alcohol.

The reaction for introducing these aralkylating agents can be performed in the presence of an acid catalyst. The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids. Examples include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, and diethyl sulfuric acid; or zinc chloride, Lewis acids such as aluminum chloride, ferric chloride, boron trifluoride, or solid acids such as ion exchange resins, activated clay, silica-alumina, and zeolites.

In addition, by reacting a phenol novolak compound obtained by reacting a bifunctional or higher phenol with a crosslinking group and the aralkylating agent in the presence of a fluorene catalyst, a part of the hydroxyl group becomes an aralkoxy group. Examples of the rhenium catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and inorganic rhenium such as metal sodium, metal lithium, sodium carbonate, and potassium carbonate. The amount used is preferably in the range of 1 to 2 moles relative to 1 mole of the aralkylating agent. In addition, the substituent (R ¹⁸ ) may be an aryl group or an aryloxy group other than those described above. As for the introduction of these, there are phenyl-substituted phenol-like aryl-substituted phenols or phenoxyphenols as raw material phenols. Aryloxy Substituted Phenol Method.

T is any of a divalent aliphatic cyclic hydrocarbon group or a divalent cross-linking group represented by the formula (3a) or the formula (3b).

The carbon number of the divalent aliphatic cyclic hydrocarbon group is preferably 5 to 15, and more preferably 5 to 10. Specific examples include a cycloalkylene group having 5 to 12 carbon atoms or a divalent group containing a condensed ring represented by the following structural formula, but the invention is not limited to these. In addition, the cycloalkylene group having 5 to 12 carbon atoms may have a different number of carbon atoms or ring members. In addition to the need for a substituent, the description of the cycloalkylene group described in X ² can be referred to.

[Chemical 9]

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

In formula (3b), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. A ² is an aromatic group containing a benzene ring, a naphthalene ring, or a biphenyl ring. These rings constituting A ² may be substituted with the same substituents as A ¹ . k is 1 or 2, and represents the number of hydroxyl groups of the raw material phenols. m represents the number of repetitions and ranges from 1 to 20. The average value is 1.5 or more, preferably 1.7 to 10, more preferably 2.0 to 5.0, and even more preferably 2.2 to 4.0.

The novolak phenol compound (b2) is preferably a phenol novolak compound containing a substituent represented by the formula (4). In formula (4), R ⁷ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, preferably methyl, t-butyl, phenyl, cyclohexyl, and the like, and more preferably methyl. R ⁸ represents a substituent represented by the 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, and more preferably 1.0 to 1.5. q is an integer of 0 to 2, and its average value is a number of 0 to 2, preferably 0 to 1. In addition, p + q is a number of 0.1 to 3 as an average value.

In 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, and more preferably a hydrogen atom or methyl. More preferably, one of R ⁹ and R ¹⁰ is a hydrogen atom, and the other is a methyl group. Specific examples of R ⁸ include benzyl, methylbenzyl, ethylbenzyl, isopropylbenzyl, tert-butylbenzyl, cyclohexylbenzyl, phenylbenzyl, and dimethylbenzyl. , 1-phenylethyl, 1-tolylethyl, 1-xylylethyl, 2-phenylpropane-2-yl, 2-tolylpropane-2-yl, 2-xylylpropane- 2-based and so on.

The phenol novolak compound represented by the formula (4) is preferably a styrene-modified novolak resin represented by the following formula (7) in which styrene is added to a phenol novolak resin. In formula (7), p and m have the same meanings as p and m in formula (4). [Chemical 10]

Examples of the raw material phenols used to obtain the novolac phenol compound (b2) include phenol, cresol, ethylphenol, butylphenol, phenylphenol, styrenated phenol, cumylphenol, and benzylphenol , Phenoxyphenol, naphthol, catechol, resorcinol, naphthalene, and the like, but are not limited to these, and these phenols may be used alone or in combination of two or more. Among these phenols, monophenols such as phenol and alkylphenol are preferred. The alkyl group in the case of alkylphenol is preferably an alkyl group having 1 to 6 carbon atoms. In addition, as described above, in the case of phenylphenol, cumylphenol, styrenated phenol, benzylphenol, or phenoxyphenol, a compound that has been novolacized with a crosslinking agent directly becomes a phenolic compound. Varnish phenol compound (b2). In other cases, it is necessary to use an aralkylating agent or the like to add a substituent such as an aralkyl group containing an aromatic ring.

Examples of the crosslinking agent that provides T of formula (3) include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and benzaldehyde, or acetone, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketones and acetophenone, or diols such as p-xylene glycol, p-xylene glycol dimethyl ether, 4,4'-dimethoxymethylbiphenyl, dimethoxymethylnaphthalene Such as dialkoxy, or dichloromethyl such as p-xylene dichloride, 4,4'-dichloromethylbiphenyl, dichloromethylnaphthalene, or divinylbenzene, divinyl Divinyls such as biphenyls and divinylnaphthalenes, or cycloalkadienes such as cyclopentadiene or dicyclopentadiene, but are not limited to these. These crosslinking agents can be used alone. Two or more kinds may be used in combination. T of the formula (3) becomes a divalent aliphatic cyclic hydrocarbon group when a cyclic diene is used, and when a aldehyde or a ketone is used, T becomes a crosslinking group represented by the formula (3a). When a glycol body, a dialkoxy body, a dichloromethyl body, or a divinyl body is used, it becomes a crosslinking group represented by Formula (3b). Among these crosslinking agents, formaldehyde, acetaldehyde, benzaldehyde, acetone, p-xylene dichloride, 4,4'-dichloromethylbiphenyl are preferred, and formaldehyde is particularly preferred. As a preferable aspect when using formaldehyde for a reaction, a formalin aqueous solution, p-formaldehyde, trioxane, etc. are mentioned.

The molar ratio of phenols to the cross-linking agent is expressed by the molar ratio of phenols to the cross-linking agent 1 mol (phenol / crosslinking agent), and the molar ratio is 0.1 or more. Manufacturing, when the mole ratio is large, a large number of dinuclear bodies and trinuclear bodies are generated, and when the mole ratio is small, a large number of high molecular weight bodies, such as dinuclear bodies and trinuclear bodies, are generated. Body becomes less. Here, in the novolak phenol compound (b2) represented by the formula (3), the nucleus such as a dinuclear body and a trinuclear body refers to the number of A ¹ existing in the molecule. That is, the i-nucleus is a compound having a structural formula of m = i-1 in formula (3). The molar ratio (phenols / crosslinking agent) of the phenols and the crosslinking agent is preferably 0.1 to 10, more preferably 0.3 to 6, and even more preferably 0.5 to 4. In addition, a novolak phenol compound having a narrow molecular weight distribution can also be obtained by reducing or removing a low molecular weight component as necessary. In this case, as a method for reducing or removing a low molecular weight component, especially a dinucleotide, a method using various solvents having poor solubility, a method of dissolving in an alkaline aqueous solution, and other known separation methods are mentioned.

Acidic catalysts used to obtain the novolac phenol compound (b2) include protonic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, toluenesulfonic acid, boron trifluoride, aluminum chloride, tin chloride, and chlorination. Lewis acids such as zinc and ferric chloride, oxalic acid, monochloroacetic acid, and the like are not limited to these. These acid catalysts may be used alone or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid, and oxalic acid are preferred.

The epoxy resin (A) in the epoxy resin composition of this invention can also use together the epoxy resin (A) other than the epoxy resin (a) containing an oxazolidone ring within the range which does not impair physical properties. The epoxy resin other than the oxazolidone ring-containing epoxy resin (a) that can be used in combination is not particularly limited, and a polyfunctional epoxy resin containing two or more epoxy groups is preferred. Specific examples include, but are not limited to, polyglycidyl ether compounds, polyglycidylamine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, or two or more epoxy resins of the same system may be used in combination, and epoxy resins of different systems may be used in combination. In the epoxy resin (A), the amount of the epoxy resin other than these oxazolidone ring-containing epoxy resins (a) is 0% to 95% by mass, and preferably 0% to 80% by mass. It is more preferably 0% by mass to 50% by mass, and still more preferably 0% by mass to 30% by mass.

Specific examples of the polyglycidyl ether compound include bisphenol A epoxy resin, bisphenol F epoxy resin, tetramethylbisphenol F epoxy resin, biphenol epoxy resin, and p-benzene. Diphenol epoxy resin, bisphenol fluorene epoxy resin, naphthalene diphenol epoxy resin, bisphenol S epoxy resin, diphenyl sulfide epoxy resin, diphenyl ether epoxy resin, Resorcinol epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alkyl novolac epoxy resin, aromatic modified phenol novolac epoxy resin, bisphenol novolac Type epoxy resin, naphthol novolac type epoxy resin, β-naphthol aralkyl type epoxy resin, naphthalene diphenol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, Benzoaralkylphenol epoxy resin, trihydroxyphenylmethane epoxy resin, tetrahydroxyphenylethane epoxy resin, dicyclopentadiene epoxy resin, alkanediol epoxy resin, fat Group cyclic epoxy resins and the like are not limited to these.

Specific examples of the polyglycidylamine compound include diaminodiphenylmethane type epoxy resin, m-xylylenediamine type epoxy resin, and 1,3-bisaminomethylcyclohexane type epoxy resin. , Isocyanurate-type epoxy resin, aniline-type epoxy resin, hydantoin-type epoxy resin, aminophenol-type epoxy resin, and the like, but are not limited to these.

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

Examples of the alicyclic epoxy compound include, but are not limited to, aliphatic cyclic epoxy resins such as Celloxide 2021 (manufactured by Daicel Chemical Industry Co., Ltd.).

Specific examples of other modified epoxy resins include urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins having a skeleton other than (a), and epoxy-modified polybutadienes. Ene rubber derivatives, CTBN modified epoxy resins, polyvinyl aromatic hydrocarbon polyoxides (eg, divinylbenzene dioxide, trivinylnaphthalene trioxide, etc.), phosphorus-containing epoxy resins, etc., but not Limited to these.

The hardener (B) in the epoxy resin composition of this invention can also use hardener other than a bisphenol compound (b1) and a novolak phenol compound (b2) in the range which does not impair physical properties. Hardeners other than (b1) and (b2) that can be used in combination are not particularly limited, and are not particularly limited as long as they harden epoxy resins, and phenol-based hardeners, acid anhydride-based hardeners, and amine-based hardeners can be used , Hardeners for epoxy resins such as hydrazine-based hardeners, active ester-based hardeners, and phosphorus-containing hardeners. These hardeners may be used alone, or two or more hardeners of the same system may be used in combination, and hardeners of different systems may be used in combination. In the hardener (B), the amount of the hardeners other than (b1) and (b2) used is 0 mass% to 95 mass%, preferably 0 mass% to 80 mass%, and more preferably 0 mass% to 50 It is more preferably 0% by mass to 30% by mass.

The phenolic hardener is particularly preferably one containing a large amount of aromatic skeleton in its molecular structure. Examples include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthalene Phenolic aralkyl resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotris Azine modified phenol resin. Among these, the same as the formula (3) is regarded as (b2), and therefore it is preferably an unsubstituted body, an alkyl substituted body, a cycloalkyl substituted body, or an alkoxy substituted body.

In addition, a benzoxazine compound that becomes a phenol compound by ring opening upon heating is also useful as a hardener. Specific examples include bisphenol F-type or bisphenol S-type benzoxazine compounds, but are not limited to these.

Specific examples of the acid anhydride-based hardener include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and orthophthalic anhydride. Phthalic anhydride, trimellitic anhydride, hydrogenated trimellitic anhydride, methylnadic anhydride, succinic anhydride, maleic anhydride, etc., or 4,4'-oxydiphthalic anhydride, 4,4 ' -Diphthalic anhydride, pyromellitic anhydride, hydrogenated pyromellitic anhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetra Carboxylic dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 4- (2,5-dioxo Tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride and the like are not limited thereto.

Examples of the amine-based hardener include amine compounds that can be used as the various epoxy resin modifiers. Other examples include 2,4,6-tris (dimethylaminomethyl) phenol, dimer diamine, dicyandiamine and its derivatives, or acids and polyamines such as dimer acids The amine-based compound such as polyamine and the like is not limited to these.

Specific examples of the hydrazine-based hardener include, but are not limited to, dihydrazide adipate, dihydrazide isophthalate, dihydrazide sebacate, and dihydrazide dodecanedioate. To these.

Examples of the active ester-based hardener include a reaction product of a polyfunctional phenol compound and an aromatic carboxylic acid as described in Japanese Patent No. 5152445, and a commercially available product is Epiclon HPC-8000-65T (Diesen (DIC) Co., Ltd.), but not limited to these.

Regarding the ratio of the epoxy resin (A) to the hardener (B), the active hydrogen group of the hardener (B) is preferably 0.2 mole to 1.5 with respect to 1 mole of the epoxy group of the epoxy resin (A). Mor. When the active hydrogen group is less than 0.2 mol or more than 1.5 mol with respect to 1 mol of epoxy group, there is a concern that hardening becomes incomplete and good hardened physical properties cannot be obtained. The preferred range is 0.3 to 1.5 mol, the more preferred range is 0.5 to 1.5 mol, and the more preferred range is 0.8 to 1.2 mol. The epoxy resin (a) containing the oxazolidone ring or the epoxy group (a2) containing the reaction product (a2) of the by-product and the like with the oxazolidone ring-containing epoxy resin (a) is 1 mole. In other words, the total of the phenolic hydroxyl groups of the bisphenol compound (b1) and the novolac phenol compound (b2) is preferably 0.8 mol to 1.2 mol, more preferably 0.9 mol to 1.1 mol, and still more preferably 0.95 mol to 1.05 moles. In the epoxy resin composition, an epoxy resin other than the oxazolidone ring-containing epoxy resin (a) or the reaction product (a2), or a bisphenol compound (b1) and a novolac phenol compound (b2) are used in combination. In the case of other hardeners, it is preferred to determine the blending amount in consideration of the most preferred blending amount of the epoxy resin or hardener used in combination. For example, when a phenol-based hardener, an amine-based hardener, or an active ester-based hardener is used in combination, a substantially equal active hydrogen group is prepared for the epoxy group, and when an acid anhydride-based hardener is used, it is relatively An acid anhydride group of 0.5 mol to 1.2 mol, preferably 0.6 mol to 1.0 mol is prepared at 1 mol of epoxy group.

The active hydrogen group referred to in this specification is a functional group having an active hydrogen reactive with an epoxy group (a functional group having a potential active hydrogen that generates active hydrogen due to hydrolysis or the like, or a function exhibiting an equivalent hardening effect) Group), specifically, an acid anhydride group, a carboxyl group, an amino group, or a phenolic hydroxyl group. Regarding the active hydrogen group, a carboxyl group (-COOH) or a phenolic hydroxyl group (-OH) was calculated as 1 mole, and an amino group (-NH ₂ ) was calculated as 2 moles. If the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, the activity of the hardener used can be determined by reacting a single epoxy resin with a known epoxy equivalent such as phenyl glycidyl ether with a hardener whose active hydrogen equivalent is unknown. Hydrogen equivalent.

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

The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton. Examples include: 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole Alkyl-substituted imidazole compounds such as 2,2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole, or 2-phenylimidazole, 2-phenyl-4-methylimidazole , 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2'-Cyanoethyl) imidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole and the like are substituted with an aryl or aralkyl-containing hydrocarbon group containing a cyclic structure such as an imidazole compound Etc., but it is not limited to these.

Examples of tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo [5.4. 0] -7-undecene (1,8-diaza-bicyclo [5.4.0] -7-undecene, DBU), etc., but it is not limited to these.

Examples of the phosphines include, but are not limited to, triphenylphosphine, tricyclohexylphosphine, and triphenylphosphinetriphenylborane.

Examples of the metal compound include, but are not limited to, tin octoate.

Examples of the amine complex salt include boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, Boron trifluoride chlorophenylamine complexes, boron trifluoride benzylamine complexes, boron trifluoride aniline complexes, or mixtures of these complexes, etc. But it is not limited to these.

Among these hardening accelerators, when used as a build-up material or a circuit board, in terms of excellent heat resistance, dielectric properties, solder resistance, and the like, 2-dimethylaminopyridine, 4 -Dimethylaminopyridines or imidazoles. When used as a semiconductor sealing material, triphenylphosphine or DBU is preferred in terms of excellent hardenability, heat resistance, electrical characteristics, and moisture resistance reliability.

The blending amount of the curing accelerator may be appropriately selected according to the purpose of use, and it is used in an amount of 0.01 to 15 parts by mass based on 100 parts by mass of the epoxy resin component in the epoxy resin composition as necessary. It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.1 to 5 parts by mass. By using a hardening accelerator, the hardening temperature can be reduced or the hardening time can be shortened.

An organic solvent or a reactive diluent may be used in the epoxy resin composition for adjusting the viscosity.

Examples of the organic solvent include amines such as N, N-dimethylformamide and N, N-dimethylacetamide, or ethylene glycol monomethyl ether and dimethoxydiethylene glycol. , Ethers such as ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or methanol Alcohols such as ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diethylene glycol, pine oil, or butyl acetate Ester, methoxybutyl acetate, methyl cellosolve acetate, celloacetate, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl Acetates such as alcohol acetate, or benzoates such as methyl benzoate, ethyl benzoate, or cellosolvants such as methyl cellosolve, cellosolve, and butyl cellosolve, or methylcarbine Carbitols such as alcohol, carbitol, butylcarbitol, or aromatic hydrocarbons such as benzene, toluene, and xylene, or dimethyl sulfene, acetonitrile, N-methylpyrrolidone, etc., but it is not limited To these.

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. , Or resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol Difunctional glycidyl ethers such as glycidyl ether, propylene glycol diglycidyl ether, or glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythritol polyglycidyl ether Polyfunctional glycidyl ethers, glycidyl esters such as glycidyl neodecanoate, and glycidylamines such as phenyldiglycidylamine and tolyldiglycidylamine are not limited thereto.

These organic solvents or reactive diluents are preferably used singly or as a mixture of a plurality of nonvolatile components at 90% by mass or less, and the appropriate type or amount can be appropriately selected depending on the application. For example, in printed wiring board applications, a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol, is preferred, and the amount used is preferably 40 mass in terms of non-volatile components. % To 80% by mass. In addition, for adhesive film applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferably used. The use amount thereof is preferably 30% by mass to 60% by mass in terms of nonvolatile components.

In the epoxy resin composition, in order to improve the flame retardancy of the obtained hardened | cured material, conventionally well-known various flame retardants can be used in the range which does not reduce reliability. Examples of usable flame retardants include halogen flame retardants, phosphorus flame retardants (phosphorus compounds as flame retardants), nitrogen flame retardants, silicone flame retardants, and inorganic flame retardants. Agent, organic metal salt-based flame retardant, etc. From the viewpoint of the environment, a halogen-free flame retardant is preferred, and a phosphorus-based flame retardant is particularly preferred. These flame retardants are not particularly limited in use, and can be used alone, or multiple flame retardants of the same system can be used, and flame retardants of different systems can also be used in combination.

As the phosphorus-containing additive, any of an inorganic phosphorus-based compound and an organic phosphorus-based compound can be used. Examples of the inorganic phosphorus-based compound include, but are not limited to, ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and nitrogen-containing inorganic phosphorus-based compounds such as phosphatidamine. .

Examples of the organic phosphorus-based compound include general organic phosphorus-based compounds such as phosphate ester compounds, condensed phosphates, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, orthophosphine compounds, or nitrogen-containing organic phosphorus-based compounds, or In addition to phosphonic acid metal salts and the like, examples thereof include phosphorus compounds having an active hydrogen group directly bonded to a phosphorus atom (for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Phenylphosphine oxide, etc.) or phosphorus-containing phenol compounds (such as 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinohydroquinone, diphenylphosphino-1,4-dioxynaphthalene, Organophosphorus compounds such as 1,4-cyclooctylene phosphinyl-1,4-phenyldiol, 1,5-cyclooctylene phosphinyl-1,4-phenyldiol, etc.), or Derivatives and the like obtained by reacting these organophosphorus compounds with compounds such as epoxy resins and phenol resins, but are not limited to these.

Examples of phosphorus-containing epoxy resins that can be used in combination include, for example, Alberto FX-305, FX-289B, TX-1320A, TX-1328 (the above are manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), etc., But it is not limited to these. The epoxy equivalent of the phosphorus-containing epoxy resin that can be used in combination 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. In addition, as the phosphorus-containing hardener that can be used in combination, in addition to the phosphorus-containing phenol compound, a production method such as that described in Japanese Patent Publication No. 2008-501063 or Japanese Patent No. 4548547 can be used. Reacts with aldehydes and phenol compounds to obtain phosphorus-containing phenol compounds. In addition, an aromatic carboxylic acid can be further reacted by the production method shown in Japanese Patent Laid-Open No. 2013-185002 to obtain a phosphorus-containing active ester compound from a phosphorus-containing phenol compound. In addition, a phosphorus-containing benzoxazine compound can be obtained by a production method shown in WO2008 / 010429.

The blending amount of the phosphorus compound that can be used in combination can be appropriately selected depending on the type of the phosphorus compound, the phosphorus content rate, the components of the epoxy resin composition, and the degree of desired flame retardancy. When the phosphorus compound is a reactive phosphorus compound, that is, a phosphorus-containing epoxy resin or a phosphorus-containing hardener, the amount of the compound is adjusted relative to the amount of epoxy resin, epoxy resin hardener, flame retardant, and other fillers or additives. The solid content (non-volatile content) in the entire epoxy resin composition is preferably 0.2% to 6% by mass, more preferably 0.4% to 4% by mass, and still more preferably 0.5% by mass. % To 3.5% by mass or less, more preferably 0.6 to 3% by mass or less. If the phosphorus content is small, there is a concern that it may become difficult to ensure flame retardancy, and if the phosphorus content is too large, there is a concern that heat resistance may be adversely affected. When the phosphorus compound is an additive-based phosphorus-based flame retardant, the solid component (non-volatile component) in the epoxy resin composition is 100 parts by mass, and when red phosphorus is used, it is preferably 0.1 part by mass It is blended in the range of ～ 2 parts by mass. In the case of using an organic phosphorus-based compound, it is preferably blended in the range of 0.1 to 10 parts by mass, and particularly preferably in the range of 0.5 to 6 parts by mass. .

When a phosphorus compound is used as the flame retardant, as the flame retardant auxiliary, for example, hydrotalcite, magnesium hydroxide, a boron compound, zirconia, calcium carbonate, zinc molybdate, and the like may be used in combination.

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, phenothiazine, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred. The blending amount of the nitrogen-based flame retardant can be appropriately selected according to the type of the nitrogen-based flame retardant, other components of the epoxy resin composition, and a desired degree of flame retardancy, and for example, a solid content in the epoxy resin composition (Non-volatile matter) It is preferable to mix | blend within the range of 0.05-10 mass parts, and it is especially preferable to mix | blend within the range of 0.1-5 mass parts. When a nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

The silicone flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom. Examples thereof include, but are not limited to, silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone-based flame retardant can be appropriately selected according to the type of the silicone-based flame retardant, other components of the epoxy resin composition, and a desired degree of flame retardancy. It is preferable to mix | blend in 100 mass parts of solid content (non-volatile matter) in the range of 0.05-20 mass parts. When a silicone flame retardant is used, a molybdenum compound, alumina, or the like 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 glass. The blending amount of the inorganic flame retardant can be appropriately selected according to the type of the inorganic flame retardant, other components of the epoxy resin composition, and a desired degree of flame retardancy. The solid content (non-volatile content) in 100% by mass of the entire epoxy resin composition using a hardener, a flame retardant, other fillers, or additives is preferably blended in a range of 0.05 to 20 parts by mass. In particular, it is preferably blended in a range of 0.5 to 15 parts by mass.

Examples of the organometallic salt-based flame retardant include ferrocene, acetoacetone metal complexes, organometallic carbonyl compounds, organo cobalt salt compounds, organosulfonic acid metal salts, metal atoms and aromatic compounds, or heterocyclic rings. The compound in which the compound is ionic or coordinated is not limited to these. The blending amount of the organometallic salt-based flame retardant can be appropriately selected according to the type of the organometallic salt-based flame retardant, other components of the epoxy resin composition, and a desired degree of flame retardancy. The solid content (non-volatile content) of all epoxy resin compositions such as hardeners, flame retardants, and other fillers or additives for epoxy resins is preferably 0.005 to 10 parts by mass. Allocation within range.

In the epoxy resin composition, if necessary, a filler, a thermoplastic resin, or a thermosetting resin other than an epoxy resin, a silane coupling agent, an antioxidant, a release agent, a defoaming agent, Other additives such as emulsifier, thixotropic agent, lubricant, pigment, etc.

Examples of the filler include fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, and clay , Calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, carbon and other inorganic fillers, or carbon fiber, glass fiber, alumina fiber, Fibrous fillers such as aluminosilicate fibers, silicon carbide fibers, polyester fibers, cellulose fibers, aromatic polyamide fibers, ceramic fibers, or fine particle rubber. Among these fillers, those which do not decompose or dissolve due to acidic compounds such as an aqueous solution of permanganate used in the surface roughening treatment of the hardened material are preferred. In particular, fused silica or crystalline silica is easy to obtain fine particles. Particles are therefore preferred. Moreover, when the compounding quantity of a filler is especially large, it is preferable to use a fused silica. Either crushed or spherical fused silica can be used. In order to increase the blending amount of the molten silicon dioxide and suppress the increase in the melt viscosity of the molding material, it is more preferable to use mainly spherical fused silica. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the fineness distribution of the spherical silica. The filler may be treated with a silane coupling agent or an organic acid such as stearic acid. As a reason for using a filler in general, the impact resistance improvement effect of hardened | cured material, or the low linear expansion property of hardened | cured material are mentioned. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite, or magnesium hydroxide is used, it has an effect of functioning as a flame retardant additive and improving flame retardancy. When used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

When considering low linear expansion and flame retardance of a hardened | cured material, it is preferable that the compounding quantity of a filler is high. The solid content (non-volatile content) in the epoxy resin composition is preferably 1% to 90% by mass, more preferably 5% to 80% by mass, and still more preferably 10% to 60% by mass. . When there are many formulation amounts, there exists a possibility that the adhesiveness required for the use of a laminated board may fall, and there exists a possibility that a hardened | cured material may become brittle and sufficient mechanical physical property may not be obtained. In addition, if the blending amount is small, there is a concern that the impact resistance of the cured product is improved, etc., and this is not the blending effect of the filler.

The average particle diameter of the inorganic filler is preferably 0.05 μm to 1.5 μm, and more preferably 0.1 μm to 1 μm. When the average particle diameter of the inorganic filler is within this range, the fluidity of the epoxy resin composition is well maintained. The average particle diameter can be measured with a fineness distribution measuring device.

The preparation of a thermoplastic resin is effective particularly when the epoxy resin composition is molded into a sheet shape or a film shape. 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, and polyvinyl acetate. Ester resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyimide resin, thermoplastic polyimide resin, polyimide resin, polytetrafluoride Ethylene resin, polyether sulfide imine resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether fluorene resin, polyfluorene resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formaldehyde resin, etc., but It is not limited to these. In terms of compatibility with epoxy resins, phenoxy resins are preferred, and in terms of low dielectric properties, polyphenylene ether resins or modified polyphenylene ether resins are preferred.

Examples of other additives include epoxy resins other than epoxy resins such as phenol resin, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, diallyl phthalate resin, and thermosetting polyimide. Thermosetting resins, or organic pigments such as quinacridone, azo, and phthalocyanine, or inorganic pigments such as titanium oxide, metal foil-like pigments, and anti-rust pigments, or hindered amine-based, benzotriazole-based, UV absorbers such as benzophenone, or hindered phenol-based, phosphorus-based, sulfur-based, hydrazine-based antioxidants, or silane-based, titanium-based coupling agents, or stearic acid, palmitic acid, and stearic acid Release agents such as zinc, calcium stearate, leveling agents, rheology control agents, pigment dispersants, shrink inhibitors, defoamers and other additives. The blending amount of these other additives is preferably in the range of 0.01% by mass to 20% by mass with respect to the solid content (nonvolatile content) in the epoxy resin composition.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the components. Moreover, the hardened | cured material of this invention can be obtained easily by hardening by the same method as a conventionally well-known method. As a method for obtaining a cured product, the same method as that of a known epoxy resin composition can be adopted, and it can be preferably used: casting, injection, pouring, dipping, drip coating, transfer molding, compression molding, or the like, or by A method such as forming a resin sheet, a copper foil with a resin, a prepreg, and the like, laminating and heating and pressure curing to form a laminated board. The curing temperature at this time is usually in the range of 100 ° C to 300 ° C, and the curing time is usually about 10 minutes to 5 hours. Examples of the cured product include laminated cured products, cast products, molded products, adhesive layers, insulating layers, and formed hardened products such as films.

Examples of the application using the epoxy resin composition include materials for circuit boards, sealing materials, casting materials, conductive pastes, and adhesives. Examples of the circuit board material include insulating materials for circuit boards such as prepregs, resin sheets, resin-containing metal foils, resin compositions for printed wiring boards or flexible wiring boards, and interlayer insulating materials for build-up substrates. Build-up adhesive film, resist ink, etc. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-ups can be used as passive components such as capacitors or active components such as integrated circuit (IC) chips. An insulating material for a so-called substrate for built-in electronic components in a substrate is used. Among these applications, in terms of characteristics such as high flame retardancy, high heat resistance, low dielectric properties, and solvent solubility, it is preferable to use interlayer insulation for printed wiring board materials, resin compositions for flexible wiring substrates, and build-up substrates. Materials such as materials for circuit boards (laminated boards) and semiconductor sealing materials.

When the epoxy resin composition is formed into a plate shape such as a laminated plate, the filler used is preferably a fibrous filler in terms of dimensional stability, flexural strength, and the like, and more preferably glass Cloth, glass fiber felt, glass roving cloth.

By impregnating the fibrous reinforcing substrate with the epoxy resin composition, a prepreg used in a printed wiring board or the like can be prepared. As the fibrous reinforcing substrate, woven or non-woven fabrics of inorganic fibers such as glass, or polyester resins, organic resins such as polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyimide resins can be used. Cloth, but not limited to this.

The method for producing a prepreg from an epoxy resin composition is not particularly limited, and can be obtained, for example, by making a varnish-like epoxy resin composition containing the organic solvent into an organic solvent and further adjusting the organic solvent to an appropriate level. After the resin varnish is impregnated into the fibrous substrate, the resin varnish is heated and dried to semi-harden the resin component (B-stage). The heating temperature is preferably 50 ° C to 200 ° C, and more preferably 100 ° C to 170 ° C, depending on the type of the organic solvent used. The heating time is adjusted according to the type of the organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, and more preferably 3 minutes to 20 minutes. At this time, the mass ratio of the epoxy resin composition and the reinforcing substrate to be used is not particularly limited, and it is usually preferably adjusted so that the resin component in the prepreg becomes 20% by mass to 80% by mass.

In addition, the epoxy resin composition of the present invention can be molded into a sheet shape or a film shape and used. In this case, a sheet or a film can be formed by a conventionally known method. The method for manufacturing the resin sheet is not particularly limited, and can be obtained, for example, by using a reverse roll coater, a corner wheel coater, and a die coater on a supporting base film that is not dissolved in the resin varnish. The resin varnish is applied while waiting for a coater, and then the resin component is B-staged by heating and drying. In addition, if necessary, another supporting base film is laminated on the coating surface (adhesive layer) as a protective film, and dried to obtain an adhesive sheet having release layers on both surfaces of the adhesive layer.

Examples of the supporting base film include metal foils such as copper foil, polyolefin films such as polyethylene film and polypropylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, silicone film, and polymer film. Among these supporting base films, a polyethylene terephthalate film which is excellent in dimensional accuracy without defects such as chipping and is also excellent in cost is preferred. In addition, a metal foil, particularly a copper foil, which facilitates multilayering of a laminated board is preferred. The thickness of the supporting base film is not particularly limited, but it is preferably 10 μm to 150 μm, and more preferably 25 μm to 50 μm, because it has strength as a support body and is less likely to cause defective lamination.

The thickness of the protective film is not particularly limited, but is generally 5 μm to 50 μm. In addition, in order to easily peel the formed pressure-sensitive adhesive sheet, it is preferable to perform surface treatment with a release agent in advance. The thickness of the coated resin varnish is preferably 5 μm to 200 μm, and more preferably 5 μm to 100 μm, based on the thickness after drying. The heating temperature is preferably 50 ° C to 200 ° C, and more preferably 100 ° C to 170 ° C, depending on the type of the organic solvent used. The heating time is adjusted according to the type of the organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, and more preferably 3 minutes to 20 minutes.

The resin sheet obtained in this manner usually becomes an insulating adhesive sheet, but a conductive adhesive sheet can also be obtained by mixing an electrically conductive metal or metal-coated fine particles in an epoxy resin composition. . In addition, the supporting base film is peeled after being laminated on a circuit board or after being heated and hardened to form an insulating layer. If the supporting base film is peeled off after the adhesive sheet is heat-hardened, dust and the like can be prevented from being attached during the hardening step. Here, the insulating adhesive sheet is also an insulating sheet.

A resin-containing metal foil obtained by using an epoxy resin composition will be described. As the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel can be used. It is preferable to use a metal foil having a thickness of 9 μm to 70 μm. The method for producing a metal foil with a resin from a flame-retardant resin composition containing a phosphorus-containing epoxy resin and a metal foil is not particularly limited, and can be obtained, for example, by using a roll coater or the like at One side of the metal foil is coated with a resin varnish whose viscosity is adjusted for the epoxy resin composition with a solvent, and then heated and dried to semi-harden (B-stage) the resin component to form a resin layer. When the resin component is semi-cured, it can be dried by heating at 100 ° C to 200 ° C for 1 minute to 40 minutes, for example. Here, it is desirable that the thickness of the resin portion of the metal foil with a resin be 5 μm to 110 μm.

Moreover, when hardening a prepreg or an insulating adhesive sheet, the hardening method of the laminated board at the time of manufacturing a printed wiring board can be used normally, It is not limited to this. For example, when a prepreg is used to form a laminate, one or more prepregs are laminated, metal foils are arranged on one or both sides to form a laminate, and the laminate is heated under pressure. The prepreg is hardened and integrated to obtain a laminated board. Here, as the metal foil, a single, alloy, or composite metal foil such as copper, aluminum, brass, or nickel can be used.

As a condition for applying heat and pressure to the laminate, the heat and pressure may be appropriately adjusted under the condition that the epoxy resin composition is hardened. However, if the amount of pressure to be applied is too low, there may be a problem in the obtained laminate. If air bubbles remain inside and the electrical characteristics are lowered, it is desirable to pressurize under conditions that satisfy moldability. The heating temperature is preferably 160 ° C to 250 ° C, and more preferably 170 ° C to 220 ° C. The pressing pressure is preferably 0.5 MPa to 10 MPa, and more preferably 1 MPa to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. If the heating temperature is low, there is a concern that the curing reaction cannot be sufficiently performed, and if the heating temperature is high, there is a concern that thermal decomposition of the cured product may be caused. If the pressing pressure is low, air bubbles may remain inside the obtained laminated plate and the electrical characteristics may decrease. If the pressing pressure is high, the resin flows before curing, and there is a concern that a laminated plate of a desired thickness may not be obtained. In addition, if the heating and pressing time is short, there is a concern that the curing reaction cannot be sufficiently performed, and if the heating and pressing time is long, there is a concern that thermal decomposition of the cured product may be caused.

Furthermore, a multilayer board can be manufactured using the single-layer laminated board obtained as mentioned above as an inner layer material. In this case, first, an additive method or a subtractive method is used to form a circuit on the laminated board, and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. On one or both sides of the inner layer, a circuit-forming surface is formed of a prepreg or a resin sheet, an insulating adhesive sheet, or a metal foil with a resin to form an insulating layer, and a conductor layer is formed on the surface of the insulating layer. To form a multilayer board.

When an insulating layer is formed using a prepreg, one or a plurality of prepregs are arranged on the circuit formation surface of the inner layer material, and a metal foil is further arranged on the outer side to form a laminate. Then, the laminated body is integrally molded by applying heat and pressure, thereby forming a cured product of the prepreg as an insulating layer, and forming a metal foil on the outside thereof as a conductive layer. Here, as the metal foil, the same metal foil as that of a user of a laminated board used as an inner layer material can be used. The heating and press forming can be performed under the same conditions as the forming of the inner layer material. A printed wiring board can be formed by forming via holes or circuits on the surface of the multilayer laminated board formed in the above-mentioned manner by an addition method or a subtractive method. In addition, the printed wiring board is used as an inner layer material, and the above-mentioned method is repeated, whereby a multi-layered multilayer board can be further formed.

For example, when an insulating layer is formed using an insulating adhesive sheet, an insulating adhesive sheet is arranged on a circuit formation surface of a plurality of inner layers to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit formation surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is integrally molded by applying heat and pressure, thereby forming a cured product of the insulating adhesive sheet as an insulating layer, and forming a multilayered inner layer material. Alternatively, a hardened product of an insulating adhesive sheet may be formed between the inner layer material and the metal foil as the conductor layer to serve as an insulating layer. Here, as the metal foil, the same metal foil as that of a user of a laminated board used as an inner layer material can be used. The heating and press forming can be performed under the same conditions as the forming of the inner layer material.

In addition, when an epoxy resin composition is applied to a laminated board to form an insulating layer, the epoxy resin composition is applied to a thickness of preferably 5 μm to 100 μm, and then at 100 ° C. to 200 ° C., preferably 150 ° C. The sheet is formed into a sheet by heat-drying at -200 ° C for 1 minute to 120 minutes, preferably 30 minutes to 90 minutes. It is generally formed by a method called a casting method. The thickness after drying is preferably 5 μm to 150 μm, and preferably 5 μm to 80 μm. In addition, in order to obtain a sufficient film thickness and to prevent uneven coating or streaks, the viscosity of the epoxy resin composition is preferably in a range of 10 mPa · s to 40,000 mPa · s at 25 ° C, and more preferably 200. mPa · s to 30,000 mPa · s. A printed wiring board can be formed by forming via holes or circuits on the surface of the multilayer laminated board formed as described above by using an addition method or a subtractive method. In addition, the printed wiring board is used as an inner layer material, and the above-mentioned method is repeated, whereby a multi-layer laminated board can be further formed.

The sealing material obtained by using the epoxy resin composition of the present invention includes tape-shaped semiconductor wafers, liquid-filled seals, underfills, semiconductor interlayer insulation films, and the like, and can be preferably used among these. For example, as a method of forming a semiconductor package, a method of casting an epoxy resin composition, or molding the epoxy resin composition using a transfer molding machine, an injection molding machine, or the like, and heating at 50 ° C to 200 ° C 2 Hours to 10 hours to obtain a molded article.

In order to prepare the epoxy resin composition as a semiconductor sealing material, the following methods may be mentioned: an epoxy resin composition is previously mixed with a formulation agent such as an inorganic filler, if necessary, or an additive such as a coupling agent and a release agent, It is then sufficiently melt-mixed using an extruder, a kneader, a roll, or the like until it becomes homogeneous. At this time, silicon dioxide is generally used as the inorganic filler. In this case, it is preferable to mix the inorganic filler in the epoxy resin composition at a ratio of 70% to 95% by mass.

In the case where the epoxy resin composition obtained as described above is used as a tape-shaped sealing material, a method may be mentioned in which a semi-hardened sheet is produced by heating it, a sealing material tape is made, and then the sealing material is used. The adhesive tape was placed on a semiconductor wafer, heated to 100 ° C to 150 ° C to soften and mold, and completely cured at 170 ° C to 250 ° C. In the case of using as an infusion type liquid sealing material, the obtained epoxy resin composition may be dissolved in a solvent as required, and then applied to a semiconductor wafer or an electronic component to directly harden it.

The epoxy resin composition of the present invention can be further used as a resist ink. In this case, there can be mentioned a method in which an epoxy resin composition is prepared by blending an ethylene-based monomer having an ethylenically unsaturated double bond, a cationic polymerization catalyst as a hardener, and further adding a pigment, talc, and a filler. After the composition for a resist ink is formed, it is applied on a printed circuit board by a screen printing method, and then a cured resist ink is produced. The curing temperature at this time is preferably a temperature range of about 20 ° C to 250 ° C.

When the epoxy resin composition of the present invention is prepared and cured by heating and evaluated, as a result, it is possible to obtain a cured product that exhibits low dielectric properties that are absent, and is excellent in a balance of heat resistance and adhesion. In addition, by blending a flame retardant, low-dielectric properties can be exhibited, and flame resistance can be imparted without deteriorating heat resistance, adhesion, and the like. [Example]

The present invention will be specifically described by citing examples and comparative examples, but the present invention is not limited to these examples, as long as it does not exceed the gist thereof. Unless otherwise specified, parts represent parts by mass and% represents mass%. An analysis method and a measurement method are shown below.

(1) Epoxy equivalent: According to Japanese Industrial Standard (JIS) K7236. (2) Softening point: Measured in accordance with JIS K7234 standard and ring and ball method. Specifically, an automatic softening point device (manufactured by Mintec Corporation, ASP-MG4) was used. (3) Glass transition temperature: in accordance with the IPC-TM-650 2.4.25.c specification, using a differential scanning calorimeter (manufactured by Hitachi High-tech Co., Ltd., EXSTAR6000 DSC6200) under a temperature rising condition of 20 ° C / min The DSC · Tgm (the intermediate temperature of the variation curve with respect to the tangent between the glass state and the rubber state) at the time of measurement is shown. (4) Peel strength and interlayer adhesion: measured in accordance with JIS C6481. Interlayer adhesion was measured by peeling between the 7th and 8th layers. (5) Relative dielectric constant and dielectric loss tangent: According to the IPC-TM-650 2.5.5.9 specification, a material analyzer (manufactured by Agilent Technologies) was used to obtain a dielectric frequency of 1 GHz using the capacitance method Constant and dielectric loss tangent. (6) Flame retardancy: It is evaluated by the vertical method in accordance with UL94. Evaluations are marked with V-0, V-1, and V-2.

Synthesis Example 1 A glass separable flask equipped with a stirring device, a thermometer, a nitrogen introduction device, a condenser, and a dropping device was charged with 100 parts of TX-1468 (the epoxy resin represented by the formula (5) , Manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., with an epoxy equivalent of 219) and 0.11 part of tetramethylammonium iodide. The temperature was raised while nitrogen was introduced, and the temperature was maintained at 120 ° C for 30 minutes to remove water in the system. Next, while maintaining a reaction temperature of 130 ° C to 140 ° C, while heating to 60 ° C, it took 3 hours to dropwise add 11.5 parts of diphenylmethane diisocyanate (NCO concentration: 34%). After the dropwise addition was completed, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (resin 1). The oxazolidone ring modification ratio (Rox) of the obtained resin 1 was 0.2, the epoxy equivalent was 300, and the softening point was 85 ° C.

Synthesis Example 2 The same device as Synthesis Example 1 was charged with 100 parts of TX-1468 and 0.12 parts of tetramethylammonium iodide. The temperature was raised while nitrogen was introduced, and the temperature was maintained at 120 ° C for 30 minutes to remove the contents of the system. Moisture. Next, while maintaining the reaction temperature of 140 ° C to 150 ° C, it took 5 hours to dropwise add a mixture of toluene diisocyanate (2,4-toluene diisocyanate (80%) and 2,6-toluene diisocyanate (20%), NCO The concentration is 48%) 17.8 parts. After the completion of the dropwise addition, stirring was continued for 60 minutes while maintaining the same temperature to obtain an epoxy resin (resin 2) containing an oxazolidone ring. The modification ratio (Rox) of the obtained resin 2 was 0.45, the epoxy equivalent was 464, and the softening point was 125 ° C.

Synthesis Example 3 The same device as Synthesis Example 1 was charged with 100 parts of TX-1468 and 0.12 parts of tetramethylammonium iodide. The temperature was raised while nitrogen was introduced, and the temperature was maintained at 120 ° C for 30 minutes to remove the contents of the system. Moisture. Next, while maintaining the reaction temperature of 140 ° C to 150 ° C, 16.0 parts of cyclohexane-1,3-diylbismethylene diisocyanate (NCO concentration: 43%) was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was continuously stirred for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (resin 3). The modification ratio (Rox) of the obtained resin 3 was 0.36, the epoxy equivalent was 400, and the softening point was 115 ° C. In addition, the content (% by mass) of the unreacted epoxy resin was 49% for resin 1, 20% for resin 2, and 33% for resin 3.

Synthesis Example 4 In the same apparatus as Synthesis Example 1, 91 parts of 4,4 '-(4-methylcyclohexylene) bisphenol, 358 parts of epichlorohydrin, and 4 parts of ion-exchanged water were charged, while stirring. The temperature was raised to 50 ° C. After uniform dissolution, 5.3 parts of a 49% aqueous sodium hydroxide solution was charged and reacted for 3 hours. Next, after raising the temperature to 64 ° C, the pressure was reduced to the extent that water refluxed. 48 hours of 49% sodium hydroxide aqueous solution was added dropwise over 3 hours, and the distilled water and epichlorohydrin were separated and refluxed by a separation tank during the dropwise addition. The epichlorohydrin was returned to the reaction vessel, and water was removed from the system to perform the reaction. After completion of the reaction, the temperature was raised to 70 ° C to perform dehydration, and the remaining epichlorohydrin was recovered by setting the temperature to 135 ° C. The pressure was returned to normal pressure, and 204 parts of methyl isobutyl ketone (MIBK) was added to dissolve. 127 parts of ion-exchanged water was added, and the solution was stirred and left to dissolve by-product salt in water to remove it. Next, 2.9 parts of a 49% aqueous sodium hydroxide solution was charged, and the reaction was stirred at 80 ° C. for 90 minutes to perform a purification reaction. MIBK was added and washed several times to remove ionic impurities. The solvent was recovered to obtain an epoxy resin (c4) in which X1 in the formula (1) was 4-methylcyclohexylene, R1 was H, and n was 0.05. The epoxy equivalent of the obtained epoxy resin (c4) was 206. Then, 100 parts of the obtained epoxy resin (c4) and 0.12 parts of tetramethylammonium iodide were charged into the same device as in Synthesis Example 1, and the temperature was raised while nitrogen was introduced, and the temperature was maintained at 120 ° C for 30 minutes. And remove water from the system. Next, 12.2 parts of diphenylmethane diisocyanate was added dropwise while maintaining the reaction temperature of 130 ° C to 140 ° C while heating to 60 ° C for 3 hours. After the dropwise addition was completed, stirring was continued for 60 minutes while maintaining the same temperature to obtain an epoxy resin (resin 4) containing an oxazolidone ring. The modification ratio (Rox) of the obtained resin 4 was 0.2, the epoxy equivalent was 290, and the softening point was 80 ° C.

Synthesis Example 5 The same apparatus as Synthesis Example 1 was charged with 86.5 parts of 4,4'-cyclohexylene bisphenol, 358 parts of epichlorohydrin, and 4 parts of ion-exchanged water, and the temperature was raised to 50 ° C while stirring. After uniform dissolution, 5.3 parts of a 49% aqueous sodium hydroxide solution was charged and reacted for 3 hours. Next, after raising the temperature to 64 ° C, the pressure was reduced to the extent that water refluxed. 48 hours of 49% sodium hydroxide aqueous solution was added dropwise over 3 hours, and the distilled water and epichlorohydrin were separated and refluxed by a separation tank during the dropwise addition. The epichlorohydrin was returned to the reaction vessel, and water was removed from the system to perform the reaction. After completion of the reaction, the temperature was raised to 70 ° C to perform dehydration, and the remaining epichlorohydrin was recovered by setting the temperature to 135 ° C. After returning to normal pressure, 204 parts of MIBK was added to dissolve. 127 parts of ion-exchanged water was added, and the solution was stirred and left to dissolve by-product salt in water to remove it. Next, 2.9 parts of a 49% aqueous sodium hydroxide solution was charged, and the reaction was stirred at 80 ° C. for 90 minutes to perform 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 X1 in the formula (1) is 4-cyclohexylene, R1 is H, and n is 0.06, and the epoxy equivalent is 200. Then, 100 parts of the obtained epoxy resin (c5) and 0.11 part of tetramethylammonium iodide were charged into the same device as in Synthesis Example 1. The temperature was raised while nitrogen was introduced, and the temperature was maintained at 120 ° C for 30 minutes. And remove water from the system. Next, while maintaining the reaction temperature of 130 ° C to 140 ° C, 12.5 parts of diphenylmethane diisocyanate was added dropwise while heating to 60 ° C for 3 hours. After the dropwise addition was completed, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (resin H1). The modification ratio (Rox) of the obtained resin H1 was 0.2, the epoxy equivalent was 285, and the softening point was 85 ° C.

Synthesis Example 6 The same device as Synthesis Example 1 was charged with 105 parts of phenol novolac (hydroxyl equivalent of 105 and softening point of 130 ° C) and 0.1 parts of p-toluenesulfonic acid, and the temperature was raised to 150 ° C. While maintaining the same temperature, 94 parts of styrene was added dropwise over 3 hours, and stirring was continued for 1 hour at the same temperature. Then, 500 parts of MIBK was added to dissolve the contents, and water washing was performed 5 times at 80 ° C. Then, MIBK was distilled off under reduced pressure to obtain a styrene-modified novolac phenol compound (APN-A). The phenolic hydroxyl equivalent of the obtained APN-A was 199, and the softening point was 110 ° C. In the formula (3), the average number of substitutions with respect to one ¹ -phenylethyl group of A ¹ is 0.9.

Synthesis Example 7 The same device as Synthesis Example 1 was charged with 105 parts of phenol novolak (phenolic hydroxyl equivalent: 105, softening point: 67 ° C) and 0.13 parts of p-toluenesulfonic acid, and the temperature was raised to 150 ° C. While maintaining the same temperature, 156 parts of styrene was added dropwise over 3 hours, and stirring was continued for 1 hour at the same temperature. Then, the same treatment as in Synthesis Example 6 was performed to obtain a styrene-modified novolac phenol compound (APN-B). The phenolic hydroxyl equivalent of the obtained APN-B was 261, and the softening point was 75 ° C. The average number of substitutions with respect to one ¹ -phenylethyl group of A ¹ was 1.5.

Synthesis Example 8 The same device as Synthesis Example 1 was charged with 210 parts of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumikin Co., Ltd., SN-475, with a phenolic hydroxyl equivalent of 210 and a softening point of 77 ° C). ), 0.18 parts of p-toluenesulfonic acid, and the temperature was raised to 150 ° C. While maintaining the same temperature, 135 parts of styrene was added dropwise over 3 hours, and stirring was continued for 1 hour at the same temperature. Then, the same treatment as in Synthesis Example 6 was performed to obtain a styrene-modified novolac phenol compound (APN-C). The phenolic hydroxyl equivalent of the obtained APN-C was 345, and the softening point was 88 ° C. The average number of substitutions with respect to one ¹ -phenylethyl group of A ¹ was 1.3.

Synthesis Example 9 The same device as Synthesis Example 1 was charged with 500 parts of phenol and 190 parts of boron trifluoride ether complex, and the temperature was raised to 120 ° C. While maintaining the same temperature, 176 parts of dicyclopentadiene was added dropwise over 6 hours, and the reaction was further performed at 130 ° C for 4 hours. Then, neutralization was performed and phenol was recovered. Further, 500 parts of MIBK was added to dissolve the contents, and water washing was performed 4 times at 80 ° C. Then, MIBK was distilled off under reduced pressure to obtain a dicyclopentadiene / phenol co-condensation resin. Then, 196 parts of the obtained dicyclopentadiene / phenol co-condensation resin and 0.11 part of p-toluenesulfonic acid were charged into the same apparatus as in Synthesis Example 1, and the temperature was raised to 150 ° C. While maintaining the same temperature, 31 parts of styrene was added dropwise over 3 hours, and stirring was continued at the same temperature for 1 hour. Then, the same treatment as in Synthesis Example 6 was performed to obtain a novolak phenol compound (APN-D) containing a substituent. The phenolic hydroxyl equivalent of the obtained APN-D was 228, and the softening point was 122 ° C. The average number of substitutions with respect to one ¹ -phenylethyl group of A ¹ was 0.3.

Synthesis Example 10 The same device as Synthesis Example 1 was charged with 500 parts of phenol and 9.5 parts of boron trifluoride ether complex, and the temperature was raised to 120 ° C. While maintaining the same temperature, 88 parts of dicyclopentadiene was added dropwise over 6 hours, and the reaction was further performed at 130 ° C for 4 hours. Then, neutralization was performed and phenol was recovered. Further, 300 parts of MIBK was added to dissolve the contents, and water washing was performed 4 times at 80 ° C. Then, MIBK was distilled off under reduced pressure to obtain a dicyclopentadiene / phenol co-condensation resin.

Then, 178 parts of the obtained dicyclopentadiene / phenol co-condensation resin and 0.11 part of p-toluenesulfonic acid were charged into the same apparatus as in Synthesis Example 1, and the temperature was raised to 150 ° C. While maintaining the same temperature, 32 parts of benzyl alcohol was added dropwise over 3 hours, and stirring was continued at the same temperature for 1 hour. Then, the same treatment as in Synthesis Example 6 was performed to obtain a novolak phenol compound (APN-E) containing a substituent. The phenolic hydroxyl equivalent of the obtained APN-E was 205, and the softening point was 90 ° C. The average number of substitutions with respect to one benzyl group of A ¹ is 0.3. The description of abbreviations used in Examples and Comparative Examples is as follows.

(Epoxy resin) (1) Epoxy resin containing oxazolidone ring (a) Resin 1 to resin 4: epoxy resin obtained in Synthesis Example 1 to Synthesis Example 4 (2) epoxy resin other than Resin resin H1: epoxy resin obtained in Synthesis Example 5 TX-1468: said YDPN-638: phenol novolac epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Epotohto YDPN- 638, epoxy equivalent is 176) KDCP-130: Dicyclopentadiene epoxy resin (manufactured by Guodu Chemical Co., Ltd., KDCP-130, epoxy equivalent is 254)

(Hardener) (1) Bisphenol compound (b1) BisP-TMC: 4,4 '-(3,3,5-trimethylcyclohexylene) bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., BisP-TMC , Phenolic hydroxyl equivalent is 155) BisP-MC: 4,4 '-(4-methylcyclohexylene) bisphenol (reagent, phenolic hydroxyl equivalent) (2) Novolac phenol compound (b2) APN-A ～ APN-E: Novolac phenol compound obtained in Synthesis Examples 6 to 10 (3) Other hardeners PN: Phenolic novolac resin (manufactured by Showa Denko Corporation, Shinol BRG-557, phenolic The hydroxyl equivalent is 105 and the softening point is 80 ° C. Bis-Z: 4,4'-cyclohexylene bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., Bis-Z, phenolic hydroxyl equivalent is 134) DCPD: dicyclopentane Diene · phenol compound (manufactured by Qunrong Chemical Co., Ltd., GDP 9140, phenolic hydroxyl equivalent is 196, and softening point is 130 ° C)

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

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

Example 1 100 parts of resin as an epoxy resin 1, 29.0 parts of BisP-TMC as a hardener, 29.0 parts of APN-A, and 0.2 part of 2E4MZ as a hardening accelerator were prepared, and dissolved in MEK and propylene glycol An epoxy resin composition varnish was obtained in a mixed solvent in which monomethyl ether and N, N-dimethylformamide were adjusted.

The obtained epoxy resin composition varnish was impregnated in a glass cloth in a hot air loop oven at 150 ° C. The impregnated glass cloth was impregnated with the obtained epoxy composition varnish in a glass cloth (ISO7628 type, thickness 0.16 mm). )in. The impregnated glass cloth was dried in a 150 ° C hot air loop oven to obtain a prepreg. 8 pieces of the obtained prepreg were laminated with copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness: 35 μm), and the temperature was 130 ° C × 15 minutes + 190 ° C × 80 minutes for 2 Vacuum compression of MPa yields a 1.6 mm thick laminated board. Table 1 shows the results of the glass transition temperature, copper foil peel strength, and interlayer adhesion of the laminated board.

In addition, the obtained prepreg was unraveled, and a sieve was passed through a 100-mesh powdery prepreg powder. This prepreg powder was put into a fluororesin mold, and vacuum-pressed at 2 MPa under a temperature condition of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes to obtain a 50 mm square × 2 mm thick test piece. Table 1 shows the results of the relative dielectric constant and dielectric loss tangent of the test piece.

Examples 2 to 8 were prepared at the compounding amount (parts) in Table 1, and the same operation was performed using the same device as in Example 1 to obtain a laminated plate and a test piece. The same test was performed as in Example 1, and the results are shown in Table 1. In addition, “b1 / b2 (equivalent ratio)” in the table indicates the equivalent ratio (molar ratio) of the bisphenol compound (b1) to the novolac phenol compound (b2). In addition, in all Examples and Comparative Examples, the equivalent ratio (molar ratio) of the epoxy resin (A) to the hardener (B) was 1.0.

Comparative Examples 1 to 7 were prepared at the compounding amount (parts) in Table 2, and the same operation was performed using the same device as in Example 1 to obtain a laminated plate and a test piece. The same test was performed as in Example 1, and the results are shown in Table 2.

[Table 1]

[Table 2]

Examples 9 to 12 and Comparative Examples 8 to 10 were prepared at the compounding amount (parts) in Table 3, and the same operation was performed using the same device as in Example 1 to obtain a laminated plate and a test piece. The same test was performed as in Example 1, and the results are shown in Table 3.

[table 3]

Examples 13 to 16 and Comparative Example 11 were prepared at the compounding amount (parts) in Table 4, and the same operation was performed using the same device as in Example 1 to obtain a laminated plate and a test piece. The flame retardant is formulated so that the phosphorus content of the epoxy resin composition becomes 2.5%. The same test was performed as in Example 1, and the results are shown in Table 4. Moreover, the test piece for flame retardance measurement was prepared by etching both surfaces of a laminated board, the flame retardance test was performed using the test piece, and the result is shown in Table 4.

[Table 4]

[Industrial Applicability] The epoxy resin composition and the cured product of the present invention are excellent in heat resistance, adhesion, and dielectric properties, and can be used as an epoxy resin cured product, prepreg, laminated board, and the like. Epoxy resin composition. In addition, the flame retardant-containing epoxy resin composition and its hardened material are further adjusted to have excellent flame retardancy, heat resistance, adhesion, and dielectric properties, and can be used as electronic circuit boards corresponding to recent high functional requirements. Epoxy resin composition for high-functional materials such as materials.

no

no.

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Claims (6)

An epoxy resin composition containing an epoxy resin (A) and a hardener (B), wherein the epoxy resin (A) contains an epoxy resin (c) represented by the following formula (1) and The oxazolidone ring-containing epoxy resin (a) and the hardener (B) obtained from the isocyanate compound (d) contain the bisphenol compound (b1) represented by the following formula (2) and the following formula (3) The novolac phenol compound (b2) represented; In the formula, X ¹ represents a cycloalkylene group having 5 to 8 ring members having at least one hydrocarbon group having 1 to 20 carbon atoms as a substituent; R ¹ each independently represents a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms. Halogenated hydrocarbon group, or a hydrocarbon group having 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; In the formula, X ² represents a cycloalkylene group having 5 to 8 ring members having at least one hydrocarbon group having 1 to 20 carbon atoms as a substituent; R ² independently represents a hydrogen atom, a halogen atom, and 1 to 20 carbon atoms. Halogenated hydrocarbon group, or a hydrocarbon group having 1 to 20 carbon atoms which may have a hetero atom; In the formula, A ¹ each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring. These aromatic ring groups may have a hydrocarbon group having 1 to 49 carbon atoms which may have a hetero atom as a substituent. Group having, on average, 0.1 to 2.5 aryl groups selected from 6 to 48 carbon atoms, aryloxy groups 6 to 48 carbon atoms, aralkyl groups 7 to 49 carbon atoms, and aralkoxy groups 7 to 49 carbon atoms A substituent in the group; T represents any of a divalent aliphatic cyclic hydrocarbon group or a divalent crosslinking group represented by the following formula (3a) or the following formula (3b); k represents 1 or 2; m represents Number of repetitions, the average value is above 1.5; In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; A ² It 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 20 carbon atoms which may have a hetero atom as a substituent. The epoxy resin composition according to item 1 of the scope of the patent application, wherein the mass ratio of the bisphenol compound (b1) to the novolac phenol compound (b2) is in a range of 5/95 to 95/5. The epoxy resin composition according to claim 1 or claim 2, wherein the bisphenol compound (b1) is 4,4 '-(3,3,5-trimethylcyclohexylene) bis Phenol or 4,4 '-(3,3,5,5-tetramethylcyclohexylene) bisphenol. According to the epoxy resin composition according to item 1 or item 2, the novolak phenol compound (b2) is a phenol compound represented by the following formula (4), In the formula, R ⁷ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R ⁸ is a substituent represented by the following formula (4a); p is 0.1 to 2.5 on the average, and q is a number of 0 to 2; p + q is 0.1 to 3 as an average value; m has the same meaning as m in formula (3); In the formula, R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The epoxy resin composition according to claim 1 or claim 2, wherein the active hydrogen group of the hardener (B) is 1 mole relative to the epoxy group of the epoxy resin (A). It is 0.2 mol to 1.5 mol. An epoxy resin hardened product, which is obtained by hardening the epoxy resin composition according to any one of claims 1 to 5.