CN107400198A - Composition epoxy resin and its hardening thing - Google Patents

Abstract

The present invention provides an epoxy resin composition and a cured product thereof which have excellent properties such as heat resistance, dielectric properties, and adhesive properties, and are useful for applications such as lamination, molding, casting, and bonding. The epoxy resin composition contains an epoxy resin (A) and a hardener (B), and the epoxy resin (A) contains an epoxy resin (c) represented by the following formula (1) and an isocyanate compound (d ) to obtain an epoxy resin (a) containing an oxazolidone ring, the hardener (B) contains a bisphenol compound (b1) represented by the following formula (2) and a phenolic compound represented by the following formula (3) Novolac phenolic compound (b2). X ¹ and X ² are cycloalkylene groups with hydrocarbon groups as substituents with ring members of 5 to 8, A ¹ is a benzene ring, a naphthalene ring, or a biphenyl ring, and T is a crosslinking group such as methylene [Chem. 1 ].

Description

Epoxy resin composition and its hardened product

technical field

The present invention relates to an epoxy resin composition capable of obtaining a cured product excellent in low dielectric properties, high heat resistance, high adhesiveness, and the like, and a cured product thereof.

Background technique

Due to the remarkable progress of electrical and electronic equipment, especially communication equipment for large-capacity and high-speed processing of data, the low dielectric constant, low dielectric loss tangent and other dielectric properties of electronic equipment components such as printed wiring boards and sealing materials used in these The requirements for electrical characteristics are increasingly strong. In addition, the wiring of the metal foil ensures the adhesive force by roughening the bonding surface, but for high-speed processing, there is also the problem of suppressing the roughening and maintaining the adhesive force.

As one of the uses of printed wiring boards, infrastructure equipment such as portable devices and base stations that maintain them have been required to be highly functional due to the dramatic increase in the amount of information in recent years. In portable devices, for the purpose of miniaturization, high multi-layer or finer wiring is carried out. In order to make the substrate thinner, materials with lower dielectric constant are required, and the bonding surface is reduced due to finer wiring. Therefore, it is necessary Higher bonding material. In substrates for base stations, materials with lower dielectric loss tangent are required to suppress attenuation of high-frequency signals.

Characteristics such as low dielectric constant, low dielectric loss tangent, and high adhesive force are largely derived from the structure of epoxy resin and hardener, which are the matrix resin of printed wiring boards.

It is known that hydroxyl groups generated when an epoxy resin composition is cured deteriorate the dielectric constant. Patent Document 1 discloses an oxazolidone ring-containing epoxy resin in which an oxazolidone ring is formed by a reaction between an epoxy resin and an isocyanate as one of designs in which hydroxyl groups are reduced. Examples of raw material epoxy resins include glycidylated compounds of dihydric phenols such as bisphenol A, tris(glycidyloxyphenyl)alkanes, and p-aminophenols, etc., Or a compound obtained by glycidylating novolaks such as phenol novolaks. However, none of the disclosed epoxy resins sufficiently satisfies the demand for dielectric properties due to the high functionalization in recent years, and the adhesiveness is also insufficient.

As a means of improving the dielectric properties of epoxy resins, it is effective to decrease the molar polarizability and increase the molar volume as indicated by the Clausius-Mossotti formula. Patent Document 2 discloses a dicyclopentadiene-phenol resin as a curing agent utilizing the effect of increasing the molar volume. Patent Document 3 discloses cycloalkylene bisphenols containing substituents such as 4,4'-(3,3,5-trimethylcyclohexylene)bisphenol, but does not disclose dielectric properties.

On the other hand, Patent Document 4 and Patent Document 5 disclose aromatic-modified phenol novolac as a curing agent. Although excellent in heat resistance, dielectric properties, etc., there is a problem that the adhesive force tends to be insufficient.

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 5-43655

[Patent Document 2] Japanese Patent Application Publication No. 2015-535865

[Patent Document 3] Japanese Patent Laid-Open No. 2-229181

[Patent Document 4] Japanese Patent Laid-Open No. 2010-235819

[Patent Document 5] Japanese Patent Laid-Open No. 2012-57079

Contents of the invention

[Problem to be Solved by the Invention]

Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition that has excellent properties such as low dielectric properties, high heat resistance, and high adhesiveness, and is useful in applications such as lamination, molding, casting, and bonding. and its hardening. In addition, an epoxy resin composition and a cured product thereof are provided which have good flame retardancy without deteriorating properties such as dielectric properties, heat resistance, and adhesiveness even when a flame retardant is blended.

[Technical means to solve the problem]

In order to solve the above problems, the inventors of the present invention have diligently studied low dielectric constant and low dielectric loss tangent materials. As a result, they have found that oxazolidinone containing Oxazolidone ring epoxy resin and epoxy resin composition using a combination of a specific bisphenol compound and a specific novolak phenol compound hardener to simultaneously achieve low dielectric constant and low dielectric loss tangent It has a high glass transition temperature, and furthermore, the adhesive force is also good, and the present invention has been completed. In addition, it was found that excellent flame retardancy is exhibited without deteriorating properties such as dielectric properties, heat resistance, and adhesiveness even when used in combination with a flame retardant.

That is, the present invention is a kind of epoxy resin composition, and it contains epoxy resin (A) and curing agent (B), and the feature of described epoxy resin composition is: epoxy resin (A) contains by following formula The epoxy resin (a) containing the oxazolidone ring obtained by the epoxy resin (c) represented by (1) and the isocyanate compound (d), the hardener (B) contains the following formula (2) A bisphenol compound (b1) and a novolac phenol compound (b2) represented by the following formula (3).

[chemical 1]

In the formula, X1 represents ^a cycloalkylidene having 5 to 8 ring members having at least one hydrocarbon group having 1 to 20 carbons as a substituent. R ¹ each independently represent a hydrogen atom, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbons, or a hydrocarbon group having 1 to 20 carbons which may have a heteroatom. G represents a glycidyl group. n represents the number of repetitions, and the average value is 0-5.

[Chem 2]

In the ^formula , X2 represents a cycloalkylene group having 5 to 8 ring members having at least one hydrocarbon group having 1 to 20 carbons as a substituent. R ² each independently represent a hydrogen atom, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbons, or a hydrocarbon group having 1 to 20 carbons which may have a heteroatom.

[Chem 3]

In the formula, A ¹ each independently represent an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic ring groups may also have a hydrocarbon group with a carbon number of 1 to 49 that may have a heteroatom as a substitute group, with an average of 0.1 to 2.5 selected from aryl groups with 6 to 48 carbons, aryloxy groups with 6 to 48 carbons, aralkyl groups with 7 to 49 carbons, and aralkyloxy groups with 7 to 49 carbons substituents in the group. T represents any one of a divalent aliphatic cyclic hydrocarbon group or a divalent crosslinking group represented by the following formula (3a) or the following formula (3b). k means 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 carbons which may have a heteroatom. R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. A2 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 heteroatom as a substituent.

Among the epoxy resin compositions, a preferred aspect of the present invention satisfies 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) Hexyl) bisphenol,

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

4) The active hydrogen group of a hardening|curing agent (B) is 0.2 mol - 1.5 mol with respect to 1 mol of epoxy groups of an 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 0.1-2.5, q is 0-2, p+q is 0.1-3 on average, 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 carbons.

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

[Effect of the invention]

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

detailed description

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 curing agent (B) contains a bisphenol compound (b1) and a novolac phenol compound (b2) as essential components.

The epoxy equivalent (g/eq.) of the epoxy resin (a) containing an oxazolidone ring is preferably 200-1000, more preferably 220-700, still more preferably 230-500, particularly preferably 250-400. When the epoxy equivalent is low, the content of the oxazolidone ring decreases and the concentration of hydroxyl groups in the cured product increases, which may result in a high dielectric constant. In addition, if the epoxy equivalent is high, the content of the oxazolidinone ring will increase more than necessary, and there may be many adverse effects such as deterioration of solvent solubility and increase of resin viscosity due to the effect of improving dielectric properties. In addition, there is a concern that the crosslinking density of the cured product is low, so that the modulus of elasticity decreases at the temperature of reflow soldering, etc., which may become a problem in use.

In addition, when the epoxy resin (a) containing an oxazolidone ring is used in a prepreg or a film material, the softening point is preferably 50°C to 150°C, more preferably 60°C to 135°C, and further Preferably it is 70°C to 110°C. When the softening point is low, there is a possibility that the amount of resin adhered may decrease due to the low viscosity when the glass cloth is impregnated with the resin varnish and then heated and dried in an oven. If the softening point is high, there are concerns that the viscosity of the resin will increase, impregnation in prepregs will deteriorate, or solvent solubility will deteriorate, or the diluent solvent will remain in the resin without volatilization during heating and drying. Voids and the like are generated when it is made into a laminated board, which poses a problem in use.

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

The epoxy resin (a) containing an oxazolidone ring is obtained by reaction of the epoxy resin (c) represented by said formula (1) and an isocyanate compound (d). In this reaction, epoxy groups react with isocyanate groups to form oxazolidinone rings. Typically, when a bifunctional epoxy resin and an isocyanate compound are used together, it becomes what has the structural unit shown by the following formula.

-E ¹ -O-CH ₂ -Ox ¹ -Ic ¹ -Ox ¹ -CH ₂ -O-

Here, E1 is ^a residue obtained by removing a glycidyl ether group from an epoxy resin, Ox1 is ^an oxazolidinone ring, and Ic1 is ^a residue obtained by removing an isocyanate group from an isocyanate.

In formula (1), R ¹ each independently represent a hydrogen atom, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbons, or a hydrocarbon group having 1 to 20 carbons which may have a heteroatom.

In the present specification, the hydrocarbon group that may have a heteroatom may be a heteroatom-containing hydrocarbon group in which a hydrocarbon group or a part of carbon constituting the hydrocarbon group is a heteroatom. The 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 in the middle or at the end. As the hetero atom, there are oxygen atom, nitrogen atom, sulfur atom and the like, and an oxygen atom is preferable. When the heteroatom is an oxygen atom or it is located at a 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. Additionally, heteroatoms may be located in hydroxyl-like substituents.

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

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

The hydrocarbon group having 1 to 20 carbons which may have a heteroatom may be linear, branched or cyclic, preferably an aliphatic hydrocarbon group with 1 to 20 carbons, an alicyclic hydrocarbon group with 3 to 20 carbons, Or an aromatic hydrocarbon group with 6 to 20 carbons, more preferably an alkyl group with 1 to 8 carbons, an alkoxy group with 1 to 8 carbons, a cycloalkyl group with 5 to 8 carbons, a ring with 5 to 8 carbons Alkoxy, aryl with 6 to 14 carbons, aryloxy with 6 to 14 carbons, aralkyl with 7 to 15 carbons, or aralkyloxy with 7 to 15 carbons. In these, a part of carbon may be a heteroatom.

For example, examples of alkyl or alkoxy groups 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., and examples of cycloalkyl or cycloalkoxy having 5 to 8 carbon atoms include cyclohexyl, cyclohexyloxy, etc. , as the aryl or aryloxy group having 6 to 14 carbons, include: phenyl, tolyl, o-xylyl, naphthyl, indenyl, phenoxy, naphthyloxy, etc., as the aryl group having 7 carbons ~15 aralkyl or aralkyloxy groups include: benzyl, phenethyl, 1-phenylethyl, naphthylmethyl, anthracenylmethyl, benzyloxy, naphthylmethoxy, anthracene group, methoxy group, etc., but are not limited to these, and may be the same or different.

When flame retardancy is required, it preferably has a halogen atom or a halogenated hydrocarbon group having 1 to 20 carbon atoms as a substituent, and the halogen atom is preferably a bromine atom. Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include methyl bromide 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 contained.

From the viewpoint of ease of acquisition and physical properties of a cured product, R ¹ is preferably a hydrogen atom, methyl, methoxy, phenyl, benzyl, 1-phenylethyl, or phenoxy. The substitution position of R1 is any ^one of the ortho-position, para-position, and meta-position with respect to the carbon atom bonded to X1, preferably the ortho ^- position or the para-position, and more preferably the ortho-position.

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

From the viewpoint of dielectric properties, the hydrocarbon group having 1 to 20 carbons as a substituent preferably has a large molecular weight structure, and is preferably an alkyl group having 1 to 8 carbons, a cycloalkyl group having 5 to 8 carbons, a carbon An aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms. For example, as an alkyl group having 1 to 8 carbon atoms, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, etc., as a cycloalkyl group having 5 to 8 carbon atoms, Examples include cyclohexyl, etc. Examples of the aryl group having 6 to 14 carbons include phenyl, tolyl, o-xylyl, naphthyl, etc. Examples of the aralkyl group having 7 to 15 carbons include benzyl , phenethyl, 1-phenylethyl, etc., but 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 a cured product, preferred substituents are alkyl groups having 1 to 3 carbon atoms or phenyl groups, more preferably methyl groups.

In addition, the cycloalkylene is a 1,1-cycloalkylene group, and the substituent is formed due to the steric repulsion between two benzene rings or substituents bonded to the 1-position carbon of the cycloalkylene group. Restricting the mobility of the cycloalkane ring improves the dielectric properties and also improves the heat resistance. The substitution position may be bonded at any position as long as the mobility can be restricted, but it is preferably bonded to a carbon atom close to the 1-position of the cycloalkylene group. The preferred position of the substituent is the 2- or 5-position carbon atom in the cyclopentane ring. In the cyclohexane ring, it is a carbon atom at the 2-position, 3-position, 5-position or 6-position, more preferably a carbon atom at the 2-position or 6-position. In the cycloheptane ring, it is a carbon atom at the 2-position, 3-position, 6-position or 7-position, more preferably a carbon atom at the 2-position or 7-position. In the cyclooctane ring, it is the carbon atom at the 2-position, 3-position, 4-position, 6-position, 7-position or 8-position, more preferably the carbon atom at the 2-position, 3-position, 7-position or 8-position, and more preferably 2 A carbon atom at the 8-position or 8-position. 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 1-position. In this case, the substituent is preferably bonded to the second closest carbon atom. For example, in the cyclohexane ring, the carbon atom at the 2- or 6-position is closest to the 1-position, but in the case of difficult substitution due to steric hindrance, the substituent can be bonded to the second closest 3- or 5-position .

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

In formula (1), n is the number of repetitions, and its average value (number average) is 0-5, preferably 0-3, more preferably 0-1, still more preferably 0-0.5, most preferably 0. It may be a single compound whose repetition number is any integer of 0-5, or may be a mixture in which n is a plurality of integers of 0-5.

The epoxy equivalent of the epoxy resin (c) is preferably 100-500, more preferably 125-400, and still more preferably 150-300. In addition, the alcoholic hydroxyl group equivalent (g/eq.) is preferably 3,000 or more, more preferably 4,000 or more, and still more preferably 5,000 or more. Since the alcoholic hydroxyl group reacts with isocyanate to form a urethane bond and lowers the glass transition point of the cured product, it is not preferable that the alcoholic hydroxyl group equivalent is small. In addition, since the concentration of hydroxyl groups in the cured product increases, the dielectric constant of the cured product increases, which is also not preferable.

Examples of the epoxy resin (c) include epoxy resins obtained from the cycloalkylene group-containing bisphenol compound represented by the formula (2) and epihalohydrin. For example, 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-phenylphenol glycidyl ether, 4,4'-(3,3,5-trimethylcyclohexylene)-bis-dimethylphenol glycidyl ether, 4, 4'-(3,3,5-trimethylcyclohexylene)-bis-tert-butylphenol glycidyl ether and the like are not limited thereto, and 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 An epoxy resin (c1) represented by the following formula (5) was obtained. In addition, n in formula (5) has the same meaning as n in formula (1).

[chemical 7]

When producing the above-mentioned oxazolidone ring-containing epoxy resin (a), the desired oxazolidone ring-containing epoxy resin can be obtained by reacting the epoxy resin (c) with the 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 substantially difunctional or higher polyfunctional isocyanate compound, known and commonly used ones can be used. isocyanate compounds. A small amount of monofunctional isocyanate compound may be included, but since it becomes a terminal group, it is effective for reducing the degree of polymerization, but the degree of polymerization does not become high.

Specifically, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,5-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenyl Methyl methane diisocyanate, 4,4'-diphenylmethane diisocyanate, meta-xylene diisocyanate, p-xylene diisocyanate, tetramethyl xylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5 -Naphthalenediyl diisocyanate, 2,6-naphthalenediyl diisocyanate, 2,7-naphthalenediyl diisocyanate, naphthalene-1,4-diyl bis(methylene) diisocyanate, naphthalene-1,5- Diyl bis(methylene) diisocyanate, m-phenylene diisocyanate, p-phenylene 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, diphenylsulfone-4,4 '-Diisocyanate, bicyclo[2.2.1]heptane-2,5-diylbis-methylene diisocyanate, bicyclo[2.2.1]heptane-2,6-diylbis-methylene diisocyanate, iso Phorne diisocyanate, 4,4'-methylenebiscyclohexyl diisocyanate, lysine diisocyanate, 1,1-bis(isocyanate methyl)cyclohexane, 1,2-bis(isocyanate methyl)cyclohexane Hexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, 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-trimethylhexa Methylene 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-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate , 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2,2-dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate Isocyanate, heptane-1,7-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate, dimethylsilane diisocyanate, diisocyanate Difunctional isocyanate compounds such as phenylsilane diisocyanate, or triphenylmethane triisocyanate, 1,3,6-Hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, dicycloheptane triisocyanate, tris(isocyanate phenyl)phosphorothioate, lysine Amino acid ester triisocyanate, undecane triisocyanate, tris(4-phenylisocyanate phosphorothioate)-3,3',4,4'-diphenylmethane tetraisocyanate, polymethylene polyphenylisocyanate Polyfunctional isocyanate compounds such as polyfunctional isocyanate compounds, or multimers such as dimers or trimers of said isocyanate compounds, or block-type isocyanates masked with blocking agents such as alcohols or phenols, or diurethane compounds, etc. , but not limited to these. These isocyanate compounds may be used alone or in combination of two or more.

Among these isocyanate compounds, difunctional isocyanate compounds or trifunctional isocyanate compounds are preferred, and difunctional isocyanate compounds are more preferred. When the number of functional groups of the isocyanate compound is large, the storage stability may be lowered, and if the number of functional groups of the isocyanate compound is small, the heat resistance or dielectric properties may not be improved. Further preferred isocyanate compounds are selected from 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 3,5-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diisocyanate, Phenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethylxylene diisocyanate, 1,4-naphthalenediyl diisocyanate, 1, 5-naphthalenediyl diisocyanate, 2,6-naphthalenediyl diisocyanate, 2,7-naphthalenediyl diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, isophthalic diisocyanate Isocyanate, p-phenylene diisocyanate, cyclohexane-1,4-diyl diisocyanate, cyclohexane-1,3-diyl bis-methylene diisocyanate, cyclohexane-1,4-diyl bis-methylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 4,4'-methylene Bicyclohexyl diisocyanate, bicyclo[2.2.1]heptane-2,5-diylbismethylene diisocyanate, bicyclo[2.2.1]heptane-2,6-diylbismethylene diisocyanate, and one or more of the group consisting of isophorone diisocyanate. Among these, particularly preferable isocyanate compound (d) is selected from 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-diyl bis-methylene diisocyanate, cyclohexane-1,4-di One or more of the group consisting of bis-methylene diisocyanate and isophorone diisocyanate.

The reaction of an epoxy resin (c) and an isocyanate compound (d) can be performed by a well-known method. Concrete reaction method has: (1) epoxy resin (c) is melted, and the moisture in epoxy resin is removed by the methods such as utilizing drying gas flushing or setting pressure reduction in the system, then add isocyanate compound (d) and or (2) pre-mixing the epoxy resin (c) with the catalyst, flushing with dry gas or reducing the pressure in the system to remove the moisture in the epoxy resin, and then adding the isocyanate compound (d) The method of carrying out the reaction, etc. The water content 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, when the viscosity of the resin is high and stirring is difficult, 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. Moreover, when n of formula (1) is 1 or more, alcoholic hydroxyl group which performs addition reaction with the isocyanate group of an isocyanate compound (d) and forms a urethane bond is contained. Except for the case where n in the formula (1) is 0, there are impurities added by utilizing the urethane bond. The oxazolidone ring-containing epoxy resin (a) used in the present invention includes not only an oxazolidone ring-containing epoxy resin but also a generally unreacted raw material epoxy resin (c). In addition, an impurity that undergoes an addition reaction by a urethane bond may also be contained. Even a mixture of these is included in the oxazolidone ring-containing epoxy resin (a) used in the present invention.

In addition, the epoxy equivalent (No) of the epoxy resin (a) containing an oxazolidone ring can be estimated according to the following calculation formula according to the kind of raw material, and the loading amount. In addition, on the contrary, for the epoxy resin (a) containing the oxazolidone ring of the desired epoxy equivalent, it can be determined according to the epoxy equivalent (Ne) of the epoxy resin (c) and the isocyanate group of the isocyanate compound (d). Equivalent (Ni) was calculated|required the charging amount of the epoxy resin (c) and the isocyanate compound (d) according to the following calculation formula. In addition, the unit of equivalent is g/eq. Unless otherwise specified, it is the same below.

[number 1]

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

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

For example, when the epoxy equivalent of the epoxy resin (c) is 220 and the equivalent of the isocyanate group of the isocyanate compound (d) is 125, the epoxy equivalent of the epoxy resin (a) containing an oxazolidone ring It becomes the charging amount of about 500, and the isocyanate compound (d) is 30 mass parts with respect to 100 mass parts of epoxy resins (c) from the said calculation formula.

From the viewpoint 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 has the disadvantages of The modification ratio of the oxazolidone ring is preferably 0.15 to 0.6, more preferably 0.2 to 0.5, and still more preferably 0.25 to 0.45. When the oxazolidinone ring modification rate is large, the molecule becomes a macromolecule or the viscosity increases, which may lower the solvent solubility. In addition, if the modification rate of the oxazolidinone ring is small, there will be few oxazolidinone rings with rigidity and high molecular interaction, and the effect of improving the heat resistance or adhesiveness of the hardened product will not be sufficient. There are also many hydroxyl groups, and the effect of improving the electrical characteristics is also indistinguishable. In addition, since the oxazolidone ring modification rate is substantially determined by the ratio of the epoxy group used and the isocyanate group, the oxazolidone ring modification rate is defined by the following formula in this specification.

Oxazolidinone ring modification rate = (isocyanate group mol) / (epoxy group mol)

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

As the non-reactive solvent usable by the reaction of the epoxy resin (c) and the isocyanate compound (d), specifically, hexane, heptane, octane, decane, dimethylbutane, Pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene and other hydrocarbons, or acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, Or diethyl ether, isopropyl ether, butyl ether, diisoamyl 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 Esters, propyl acetate, butyl acetate, diethyl oxalate and other esters, or N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and other amides , or lactones such as γ-butyrolactone, or sulfoxides such as dimethyl sulfoxide, or ureas such as tetramethylurea, or dichloromethane, 1,2-dichloroethane, 1,4- Halogenated hydrocarbons such as dichlorobutane, chlorobenzene, ortho-dichlorobenzene are not limited to these, and these non-reactive solvents may be used alone or in combination of two or more. The usage-amount of these solvents is preferably 1-900 mass parts with respect to 100 mass parts of epoxy resins (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 catalyst addition temperature is preferably in the range of room temperature to 150°C, more preferably in the range of room temperature to 100°C.

The reaction temperature is preferably 100°C to 250°C, more preferably 100°C to 200°C, still more preferably 120°C to 160°C. When the reaction temperature is low, the formation of the oxazolidone ring cannot proceed sufficiently, and an isocyanurate ring is formed by a trimerization reaction of isocyanate groups. In addition, when the reaction temperature is high, a local increase in molecular weight occurs, resulting in an increase in the generation of insoluble gel components. 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, an oxazolidinone ring can be formed almost 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), more preferably 30 minutes to 8 hours, and still more preferably 1 hour to 5 hours. If the reaction time is short, a large amount of isocyanate groups may remain in the product, and if the reaction time is long, there may be a possibility that productivity will be significantly lowered.

The type of the catalyst used in the reaction is not particularly limited as long as it is a basic catalyst. Specifically, lithium compounds such as lithium chloride and lithium butoxide, boron trifluoride complex salts, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, Butyl ammonium bromide, tetramethyl ammonium iodide, tetraethyl ammonium iodide, tetrabutyl ammonium iodide and other quaternary ammonium salts, dimethylaminoethanol, triethylamine, tributylamine, benzyl dimethyl tertiary amines such as base amine, N-methylmorpholine, N,N'-dimethylpiperazine, 1,4-diethylpiperazine, triphenylphosphine, tris(2,6-dimethoxy Phosphine such as phenyl) phosphine, amyl triphenyl phosphonium bromide, diallyl diphenyl phosphonium bromide, ethyl triphenyl phosphonium chloride, ethyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, Phenylphosphonium iodide, butyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, tetrabutylphosphonium acetate·acetic acid complex, tetrabutylphosphonium acetate, Phosphonium salts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium iodide, combinations of triphenylantimony and iodine, 2-phenylimidazole, 2-methylimidazole, 2-ethyl - imidazoles such as 4-methylimidazole, etc., but not limited to these, and these catalysts may be used alone or in combination of two or more. In addition, it may 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 reaction selectivity. If the catalyst is low in reactivity, the reaction time may be prolonged to lower productivity, and if the catalyst is low in reaction selectivity, the polymerization reaction between epoxy groups may proceed and target physical properties may not be obtained.

The usage-amount of a catalyst is not specifically limited, It is 0.0001 mass % - 5 mass % with respect to the total mass of an epoxy resin (c) and an isocyanate compound (d), Preferably it is 0.0005 mass % - 1 mass %, More preferably, it is 0.001% by mass to 0.5% by mass, more preferably 0.002% by mass to 0.2% by mass. Since the self-polymerization reaction of an epoxy group advances in some cases when there are many catalyst amounts, resin viscosity will become high. In addition, it promotes the self-polymerization reaction of isocyanate and suppresses the formation of oxazolidinone ring. Furthermore, there is a concern that it remains as an impurity in the produced resin, and may cause a decrease in insulation or a decrease in moisture resistance in various applications, especially when used as a material for a laminate or a sealing material.

The curing agent (B) contains the bisphenol compound (b1) represented by the formula (2) and the novolac phenol compound (b2) represented by the formula (3). The mixing ratio (b1/b2; mass ratio) of the bisphenol compound (b1) to the novolac phenol compound (b2) is preferably 5/95 to 95/5, more preferably 10/90 to 90 to 10, and still more preferably 20 /80 to 80/20, particularly preferably 30/70 to 70/30. If the epoxy resin (A) is only an epoxy resin (a) containing an oxazolidone ring, and the hardener (B) is only a mixture of a bisphenol compound (b1) and a novolac phenol compound (b2), the maximum Bring into play the effect of the present invention to the limit. Moreover, when this combination is contained in an epoxy resin composition, since the effect of content can be added compared with the case where it does not contain, a small amount of addition is possible.

The content of the epoxy resin (a) containing an oxazolidone ring in the epoxy resin (A) is preferably 5% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, still more preferably 50% by mass ~100% by mass, particularly preferably 70% by mass to 100% by mass, most preferably 100% by mass. The content of the mixture of the bisphenol compound (b1) and the novolac phenol compound (b2) in the curing agent (B) is preferably 5% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, and still more preferably 50% by mass. % by mass to 100% by mass, particularly preferably 70% by mass to 100% by mass, most preferably 100% by mass. In the case of using a reaction product containing by-products and the like as the epoxy resin (a) containing an oxazolidone ring, the content of the epoxy resin (a) containing an oxazolidone ring in the reaction product is significantly Except for a small amount (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 represent a hydrogen atom, a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbons, or a hydrocarbon group having 1 to 20 carbons which may have a heteroatom. These are the same as those described in R ¹ of the formula (1). In addition, X2 is a cycloalkylene group having ⁵ to 8 ring members, having at least one hydrocarbon group having 1 to 20 carbons as a substituent. These are the same as described in X1 of formula ( ¹ ).

The bisphenol compound (b1) can be obtained by reacting respective corresponding cycloaliphatic ketones and phenols. Specific examples of the bisphenol compound (b1) include cycloalkylene-containing bisphenol compounds shown below, but are not limited thereto. In addition, the residue obtained by removing two hydroxyphenyl groups (there may be substituents other than hydrogen) from the following bisphenol compound is X ² , which is also preferable X ¹ . Likewise the substituent for 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 methods disclosed in JP-A-4-282334 or JP-A-2015-51935, and can also be sold as commercial products. Obtain, for example can enumerate: BisP-TMC, BisOC-TMC, BisP-MZ, BisP-3MZ, BisP-IPZ, BisCR-IPZ, Bis26X-IPZ, BisOCP-IPZ, BisP-nBZ, BisOEP-2HBP (above is trade name , Honshu Chemical Industry Co., Ltd.), etc. 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 novolac phenol compound (b2) is represented by the formula (3). It is preferably represented by the above formula (4).

In the formula (3), A ¹ each independently represent an aromatic ring group selected from a benzene ring, a naphthalene ring or a biphenyl ring, and these aromatic ring groups may also have a hydrocarbon group with a carbon number of 1 to 49 that may have a heteroatom As a 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 carbons, an aryloxy group having 6 to 48 carbons, an aralkyl group having 7 to 49 carbons, or an aralkyloxy group having 7 to 49 carbons. one. The substituent (R ¹⁸ ) is preferably a group represented by the formula (4a) or phenyl, naphthyl, indenyl, 2-phenylethyl, naphthylmethyl, anthracenylmethyl, phenoxy , naphthyloxy, benzyloxy, naphthylmethoxy, more preferably benzyl, 1-phenylethyl. By having a substituent (R ¹⁸ ), physical properties of a cured product can be improved.

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 type of the substituent (R ²⁰ ). The hydrocarbon group having 1 to 49 carbon atoms which may have a heteroatom in the substituent (a1) is the same as the hydrocarbon group which may have a heteroatom described for R ¹ except that the number of carbon atoms 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 .

These substituents (R ¹⁸ ) can be introduced by making raw materials of phenols containing substituents (R ¹⁸ ), such as phenylphenol, cumylphenol, styrenated phenol, benzylphenol, and phenoxyphenol, and adding Obtained by phenolic novolakization. In this case, the number of substituents (R ¹⁸ ) of the phenols containing the substituent (R ¹⁸ ) is simply the average number of substituents (R ¹⁸ ). When adjusting the number of substituents (R ¹⁸ ), it is only necessary to use phenols containing substituents (R ¹⁸ ) in combination with unsubstituted phenols or substituted phenols containing substituents other than substituents (R ¹⁸ ). That's it.

In addition, a substituent (R ¹⁸ ) can also be introduced by using an aralkylating agent for the novolac phenol compound. In this case, the molar amount of the aralkylating agent used with respect to one aromatic ring of the novolac phenol compound is an average value of the number of substituents (R ¹⁸ ). Preferably, 0.1 mol to 2.5 mol of the aralkylating agent is added to one aromatic ring of the novolak phenol compound, more preferably 0.5 mol to 2.0 mol, still more preferably 1.0 mol to 1.5 mol.

Examples of the aralkylating agent include phenylcarbinol compounds, phenylhalomethane compounds, naphthylcarbinol compounds, naphthylhalomethane compounds, and styrene compounds. Specifically, benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl phenyl chloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl chloride, p-phenylbenzyl chloride, 5-chloromethyl acenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl yl-2-naphthalene and the nuclear-substituted isomers of these, α-methylbenzyl chloride, α,α-dimethylbenzyl chloride, benzyl methyl ether, o-methylbenzyl methyl ether, m-methylbenzyl Benzyl methyl ether, p-methyl benzyl methyl ether, p-ethyl benzyl methyl ether and their nuclear substitution isomers, benzyl ethyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether , p-methylbenzyl methyl ether and the nuclear-substituted isomers of these, benzyl alcohol, o-methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p- Isopropylbenzyl alcohol, p-tert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylcarbinol and the nuclear-substituted isomers of these, α-methylbenzyl alcohol, α,α-dimethyl benzyl alcohol, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, etc. The styrene compound may also contain small amounts of other reactive components (for example, unsaturated bond-containing components such as divinylbenzene, indene, coumarone, benzothiophene, indole, and vinylnaphthalene). These may be used individually, respectively, and may use 2 or more types together. Among these, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α- Methylstyrene, beta-methylstyrene, benzyl chloride, benzyl bromide, or benzyl alcohol.

The reaction of introducing these aralkylating agents can be carried out in the presence of an acid catalyst. As this acid catalyst, it can select suitably from well-known inorganic acid and organic acid. 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, dimethylsulfuric acid, and diethylsulfuric acid, or zinc chloride, chlorine Lewis acids such as aluminum chloride, ferric chloride, and boron trifluoride, or solid acids such as ion exchange resins, activated clay, silica-alumina, and zeolites.

In addition, by reacting a phenol novolac compound obtained by reacting a bifunctional or higher functional phenol with a crosslinking group and the aralkylating agent in the presence of a base catalyst, a part of the hydroxyl groups becomes an aralkoxy group. Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and inorganic bases such as metallic sodium, metallic lithium, sodium carbonate, and potassium carbonate. The amount used is preferably in the range of 1 mol to 2 mol with respect to 1 mol of the aralkylating agent.

In addition, the substituent (R ¹⁸ ) may be an aryl group or an aryloxy group other than those mentioned above, but for the introduction of these, there are aryl-substituted phenols such as phenylphenol or phenoxyphenols used as raw material phenols. The method of aryloxy substituted phenol.

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

The number of carbon atoms in the divalent aliphatic cyclic hydrocarbon group is preferably 5-15, more preferably 5-10. Specifically, a cycloalkylene group having 5 to 12 carbon atoms or a divalent group including a condensed ring represented by the following structural formula may be mentioned, but it is not limited thereto. In addition, the cycloalkylene group having ⁵ to 12 carbon atoms may have different carbon numbers or ring members, and the description of the cycloalkylene group described in X2 can be referred to except that no substituent is required.

[chemical 9]

In formula (3a), R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbons that may have a heterogen, preferably a hydrogen atom, an aliphatic hydrocarbon group with 1 to 20 carbons, a carbon number 3 An alicyclic hydrocarbon group with ∼20 carbon atoms, or an aromatic hydrocarbon group with 6 to 20 carbon atoms. When an aromatic ring is present in these substituents, the aromatic ring may have a hydroxyl group as a substituent.

In formula (3b), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbons. A ² is an aromatic group containing a benzene ring, a naphthalene ring or a biphenyl ring. ^In addition, these rings constituting A2 may be substituted with the same substituents as ^A1 .

k is 1 or 2, and represents the number of hydroxyl groups of the raw material phenols. m represents the number of repetitions and is 1-20. Its average value is 1.5 or more, Preferably it is 1.7-10, More preferably, it is 2.0-5.0, More preferably, it is 2.2-4.0.

The novolac phenol compound (b2) is preferably a substituent-containing phenol novolac compound represented by the formula (4). In formula (4), R ⁷ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, preferably methyl, tert-butyl, phenyl, cyclohexyl, etc., more preferably methyl. R ⁸ represents a substituent represented by the formula (4a). p is an integer of 0 to 3, has an average value of 0.1 to 2.5, preferably 0.5 to 2.0, more preferably 1.0 to 1.5. q is an integer of 0-2, the average value is a number of 0-2, Preferably it is 0-1. In addition, p+q is a number of 0.1-3 as an average value.

In formula (4a), R ⁹ , R ¹⁰ and R ¹¹ each independently represent hydrogen or a hydrocarbon group with 1 to 6 carbons, preferably a hydrogen atom, methyl, tert-butyl, or phenyl, 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 include: benzyl, ^methylbenzyl , ethylbenzyl, isopropylbenzyl, tert-butylbenzyl, cyclohexylbenzyl, phenylbenzyl, dimethylbenzyl , 1-phenylethyl, 1-tolylethyl, 1-xylylethyl, 2-phenylpropan-2-yl, 2-tolylpropan-2-yl, 2-xylylpropane- 2-base et al.

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 the phenol novolac resin. In formula (7), p and m have the same meanings as p and m in formula (4).

[chemical 10]

Examples of 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, naphthalenediol, etc., 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 alkylphenols are preferable. As the alkyl group in the case of alkylphenol, an alkyl group having 1 to 6 carbon atoms is suitable. In addition, as mentioned above, in the case of phenylphenol, cumylphenol, styrenated phenol, benzylphenol, or phenoxyphenol, the compound that has been novolakized by a crosslinking agent becomes novolac directly. Novolac phenolic compound (b2). In other cases, it is necessary to add substituents such as an aromatic ring-containing aralkyl group using an aralkylating agent or the like.

Examples of crosslinking agents that provide T in formula (3) include aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and benzaldehyde, or acetone, methyl ethyl ketone, methyl isobutyl Ketones, acetophenone and other ketones, or diols such as p-xylylene glycol, p-xylylene glycol dimethyl ether, 4,4'-dimethoxymethylbiphenyl, dimethoxymethylnaphthalene Dialkoxy bodies such as p-xylene dichloride, 4,4'-dichloromethylbiphenyl, dichloromethyl naphthalene and other dichloromethyl bodies, or divinylbenzene, divinyl Divinyl bodies such as biphenyls and divinylnaphthalene, or alkadienes such as cyclopentadiene and dicyclopentadiene, but not limited to these, these crosslinking agents can be used alone, Two or more types may be used in combination. T in formula (3) becomes a divalent aliphatic cyclic hydrocarbon group when cycloalkadienes are used, and a crosslinking group represented by formula (3a) when aldehydes or ketones are used. 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, and 4,4'-dichloromethylbiphenyl are preferable, and formaldehyde is particularly preferable. As a preferable aspect when formaldehyde is used for reaction, formalin aqueous solution, p-formaldehyde, trioxane, etc. are mentioned.

The molar ratio of phenols and cross-linking agent is represented by the molar ratio of phenols to 1 mole of cross-linking agent (phenols/cross-linking agent), and the molar ratio is 0.1 or more. When the ratio is large, a large number of dinuclear bodies and trinuclear bodies are produced, and conversely, when the molar ratio is small, a large amount of high-molecular weight bodies of pentanuclear bodies or higher is produced, and the number of dinuclear bodies and trinuclear bodies decreases. Here, in the novolac phenol compound (b2) represented by formula (3), the core of dinuclear body, trinuclear body, etc. means the number of A ¹ present in the molecule. That is, the so-called i nucleosome is a compound having the structural formula of m=i-1 in formula (3). The molar ratio of the phenols to the crosslinking agent (phenols/crosslinking agent) is preferably 0.1-10, more preferably 0.3-6, and still more preferably 0.5-4. In addition, a novolac phenol compound having a narrow molecular weight distribution can also be obtained by reducing or removing low molecular weight components as necessary. In this case, methods for reducing or removing low-molecular-weight components, especially dinuclear bodies, include a method utilizing poor solubility of various solvents, a method of dissolving in an alkaline aqueous solution, and other known separation methods. .

As the acidic catalyst used to obtain the novolak phenol compound (b2), there may be mentioned: protonic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, toluenesulfonic acid, boron trifluoride, aluminum chloride, tin chloride, chloride Lewis acids such as zinc and ferric chloride, oxalic acid, monochloroacetic acid, etc. are not limited to these, and these acidic catalysts may be used alone or in combination of two or more. Among these acidic catalysts, phosphoric acid, toluenesulfonic acid, and oxalic acid are preferable.

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

As the polyglycidyl ether compound, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, biphenol type epoxy resin, p-phenylene Diphenol type epoxy resin, bisphenol fluorene type epoxy resin, naphthalene diphenol type epoxy resin, bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, meta Hydroquinone type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alkyl novolak type epoxy resin, aromatic modified phenol novolak type epoxy resin, bisphenol novolak type epoxy resin 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, Phenylaralkylphenol type epoxy resin, trihydroxyphenylmethane type epoxy resin, tetrahydroxyphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, alkanediol type epoxy resin, fat Cyclic epoxy resin, etc., but not limited to these.

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

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

Although aliphatic cyclic epoxy resins, such as Celloxide 2021 (made by Daicel Chemical Industry Co., Ltd.), etc. are mentioned as an alicyclic epoxy compound, it is not limited to these.

As other modified epoxy resins, specifically, urethane-modified epoxy resins, oxazolidinone ring-containing epoxy resins with a skeleton other than (a), epoxy-modified polybutylene ethylene rubber derivatives, CTBN modified epoxy resins, polyvinylarene polyoxides (for example, divinylbenzene dioxide, trivinylnaphthalene trioxide, etc.), phosphorus-containing epoxy resins, etc., but not limited to these.

In the curing agent (B) in the epoxy resin composition of the present invention, a curing agent other than the bisphenol compound (b1) and the novolac phenol compound (b2) may be used in combination as long as the physical properties are not impaired. The curing agents other than (b1) and (b2) that can be used in combination are not particularly limited as long as they cure epoxy resins, and phenol-based curing agents, acid anhydride-based curing agents, and amine-based curing agents can be used , Hydrazide-based hardeners, active ester-based hardeners, phosphorus-containing hardeners and other hardeners for epoxy resins. These curing agents may be used alone, or two or more curing agents of the same system may be used in combination, or curing agents of different systems may be used in combination. In the curing agent (B), the amount of curing agents other than these (b1) and (b2) used is 0% by mass to 95% by mass, preferably 0% by mass to 80% by mass, more preferably 0% by mass to 50% by mass. % by mass, more preferably 0% by mass to 30% by mass.

The phenolic curing agent is particularly preferably one containing a large number of aromatic skeletons in the molecular structure, for example: phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthalene Phenol aralkyl resins, naphthol novolak resins, naphthol-phenol co-denatured novolac resins, naphthol-cresol co-deepized novolak resins, biphenyl modified phenol resins, biphenyl modified naphthol resins, amino tri Oxyzine modified phenol resin. Among these, what is the same as 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, benzoxazine compounds that are ring-opened to become phenolic compounds when heated are also useful as curing agents. Specifically, bisphenol F type or bisphenol S type benzoxazine compounds, etc. are mentioned, but it is not limited to these.

As the acid anhydride curing agent, specifically, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, 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 acid 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, etc., but not limited to these.

Examples of the amine-based curing agent include amine compounds that can be used as the various epoxy resin modifiers described above. Other examples include 2,4,6-tris(dimethylaminomethyl)phenol, or dimer diamine, or dicyandiamine and its derivatives, or dimer acid and other acids and polyamines. The condensate of polyamidoamine is an amine compound such as polyamidoamine, but it is not limited to these.

Examples of the hydrazide hardener include, but not limited to, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, and dodecanedioic acid dihydrazide. on these.

As the active ester hardener, the reaction products of polyfunctional phenolic compounds and aromatic carboxylic acids as described in Japanese Patent No. 5152445 can be cited, and commercially available products include Epiclon (Epiclon) HPC-8000-65T (Di DIC Co., Ltd.), etc., but are not limited to these.

The ratio of the epoxy resin (A) to the curing agent (B) is preferably 0.2 mol to 1.5 mol of active hydrogen groups in the curing agent (B) relative to 1 mol of epoxy groups in the epoxy resin (A). When the active hydrogen group is less than 0.2 mol or exceeds 1.5 mol with respect to 1 mol of the epoxy group, curing may be incomplete and favorable cured properties may not be obtained. A preferable range is 0.3 mol to 1.5 mol, a more preferable range is 0.5 mol to 1.5 mol, and a further preferable range is 0.8 mol to 1.2 mol. In addition, with respect to 1 mol of epoxy groups of the epoxy resin (a) containing an oxazolidone ring or the reaction product (a2) containing an epoxy resin (a) containing an oxazolidone ring and a by-product, etc. 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, still more preferably 0.95 mol to 1.05 mol. In the epoxy resin composition, epoxy resins other than the epoxy resin (a) or the reaction product (a2) containing an oxazolidone ring, or a bisphenol compound (b1) and a novolac phenol compound (b2) are used in combination In the case of other curing agents, it is preferable to determine the compounding amount in consideration of the most preferable compounding amount of the epoxy resin or curing agent to be used together. For example, when a phenolic curing agent, an amine curing agent, or an active ester curing agent is used in combination, approximately equimolar active hydrogen groups are prepared with respect to the epoxy group, and when an acid anhydride curing agent is used, relative to 0.5 mol to 1.2 mol, preferably 0.6 mol to 1.0 mol of acid anhydride groups are prepared per 1 mol of epoxy groups.

The so-called active hydrogen group in this specification is a functional group having an active hydrogen reactive with an epoxy group (including a functional group having a potential active hydrogen that generates active hydrogen due to hydrolysis, etc., or a functional group that exhibits an equivalent hardening effect. group), specifically, an acid anhydride group, a carboxyl group, an amino group, or a phenolic hydroxyl group. In addition, regarding the active hydrogen group, a carboxyl group (—COOH) or a phenolic hydroxyl group (—OH) is counted as 1 mole, and an amino group (—NH ₂ ) is counted as 2 moles. In addition, when the active hydrogen group is not clear, the active hydrogen equivalent can be obtained by measurement. For example, the activity of the hardener used can be obtained by reacting a monoepoxy resin with a known epoxy equivalent such as phenyl glycidyl ether with a hardener with an unknown active hydrogen equivalent and measuring the amount of monoepoxy resin consumed. hydrogen equivalent.

A hardening accelerator may be used in the epoxy resin composition of this invention as needed. Examples of the hardening accelerator include imidazole derivatives, phosphorus compounds such as tertiary amines, and phosphines, metal compounds, Lewis acids, and amine complex salts, but are not limited thereto. These curing 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 , 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole and other alkyl-substituted imidazole compounds, 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 other imidazole compounds substituted by hydrocarbon groups containing ring structures such as aryl or aralkyl etc., but not limited to these.

As tertiary amines, for example, 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 not limited to these.

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

As a metal compound, tin octylate etc. are mentioned, for example, but it is not limited to these.

Examples of the amine complex salt include: boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chloride Boron trifluoride complexes such as phenylamine complexes, boron trifluoride benzylamine complexes, boron trifluoride aniline complexes, or mixtures of these complexes, etc., but are not limited to These.

Among these hardening accelerators, 2-dimethylaminopyridine, 4-Dimethylaminopyridine or imidazoles. In addition, when used as a sealing material for semiconductors, triphenylphosphine or DBU is preferable in terms of excellent curability, heat resistance, electrical properties, moisture resistance reliability, and the like.

The compounding quantity of a hardening accelerator should just be selected suitably according to the purpose of use, and 0.01 mass part - 15 mass parts are used as needed with respect to 100 mass parts of epoxy resin components in an epoxy resin composition. Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-8 mass parts, More preferably, it is 0.1-5 mass parts. By using a hardening accelerator, the hardening temperature can be lowered, or the hardening time can be shortened.

Organic solvents or reactive diluents may be used in the epoxy resin composition for viscosity adjustment.

Examples of organic solvents include amides such as N,N-dimethylformamide and N,N-dimethylacetamide, or ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol, Alcohol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether and other ethers, or acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, or methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyldiethylene glycol, pine oil and other alcohols, or butyl acetate, acetic acid Butyl Methoxy, Methyl Cellosolve Acetate, Cellosolve Acetate, Ethyl Diethylene Glycol Acetate, Propylene Glycol Monomethyl Ether Acetate, Carbitol Acetate, Benzyl Alcohol Acetate Acetate esters such as esters, or benzoate esters such as methyl benzoate and ethyl benzoate, or cellosolves such as methyl cellosolve, cellosolve, butyl cellosolve, or methyl carbitol, carbitol, etc. Carbitols such as benzyl alcohol and butyl carbitol, or aromatic hydrocarbons such as benzene, toluene, and xylene, or dimethyl sulfoxide, acetonitrile, and N-methylpyrrolidone, are not limited thereto.

Examples of reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether. , or resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol di Glycidyl ether, propylene glycol diglycidyl ether and other difunctional glycidyl ethers, or glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythritol polyglycidyl ether Polyfunctional glycidyl ethers such as polyfunctional glycidyl ethers, or glycidyl esters such as glycidyl neodecanoate, or glycidylamines such as phenyl diglycidylamine and cresyl diglycidylamine, but are not limited to these.

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

In the epoxy resin composition, in order to improve the flame retardancy of the obtained cured product, various conventionally known flame retardants can be used within the range of not lowering the reliability. Examples of flame retardants that can be used include: halogen-based flame retardants, phosphorus-based flame retardants (phosphorus compounds as flame retardants), nitrogen-based flame retardants, silicone-based flame retardants, inorganic-based flame retardants agent, organometallic salt flame retardant, etc. From an environmental viewpoint, a halogen-free flame retardant is preferred, and a phosphorus-based flame retardant is particularly preferred. The use of these flame retardants is not particularly limited, and may be used alone, multiple types of flame retardants of the same system may be used, and flame retardants of different systems may be used in combination.

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

As organophosphorus compounds, for example, general-purpose organophosphorus compounds such as phosphoric acid ester compounds, condensed phosphoric acid esters, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, and phosphorous compounds, or nitrogen-containing organophosphorus compounds, or secondary Phosphonic acid metal salts and the like include: phosphorus compounds having an active hydrogen group directly bonded to the phosphorus atom (e.g., 9,10-dihydro-9-oxa-10-phosphinephenanthrene-10-oxide, dihydrophenanthrene-10-oxide, Phenylphosphine oxide, etc.) or phosphorus-containing phenolic compounds (such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphinephenanthrene-10-oxide, 10-(2,7- Dihydroxynaphthyl)-10H-9-oxa-10-phosphinanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalene, Organophosphorus compounds such as 1,4-cyclooctylphosphinyl-1,4-phenyldiol, 1,5-cyclooctylphosphinyl-1,4-phenyldiol, etc.), or Derivatives obtained by reacting these organophosphorus compounds with compounds such as epoxy resins and phenol resins, etc., but are not limited to these.

As phosphorus-containing epoxy resins that can be used in combination, for example: Albert (Epotohto) 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 which can be used together becomes like this. Preferably it is 200-800, More preferably, it is 300-780, More preferably, it is 400-760. The phosphorus content is preferably 0.5% by mass to 6% by mass, more preferably 2% by mass to 5.5% by mass, and still more preferably 3% by mass to 5% by mass. In addition, as a phosphorus-containing curing agent that can be used in combination, in addition to the above-mentioned phosphorus-containing phenolic compound, the production method shown in Japanese Patent Application Laid-Open No. 2008-501063 or Japanese Patent No. 4548547 can be used by making a phosphorus compound React with aldehydes and phenolic compounds to obtain phosphorus-containing phenolic compounds. In addition, a phosphorus-containing active ester compound can be obtained from a phosphorus-containing phenol compound by further reacting aromatic carboxylic acids using the production method shown in JP-A-2013-185002. In addition, a phosphorus-containing benzoxazine compound can be obtained by the production method described in WO2008/010429.

The compounding quantity of the phosphorus compound which can be used together can be suitably selected according to the kind of phosphorus compound, phosphorus content rate, the component of an epoxy resin composition, and the degree of desired flame retardancy. In the case where the phosphorus compound is a reactive phosphorus compound, that is, a phosphorus-containing epoxy resin or a phosphorus-containing hardener, compared to the compounded epoxy resin, epoxy resin hardener, flame retardant, and other fillers or additives, etc. The phosphorus content is preferably 0.2% by mass to 6% by mass or less, more preferably 0.4% by mass to 4% by mass or less, and still more preferably 0.5% by mass in terms of solid content (non-volatile matter) in the entire epoxy resin composition. % to 3.5% by mass or less, more particularly preferably 0.6 to 3% by mass or less. If the phosphorus content is small, it may become difficult to ensure flame retardancy, and if the phosphorus content is too large, there may be a bad influence on heat resistance. When the phosphorus compound is an additive phosphorus-based flame retardant, in the case of using red phosphorus in 100 parts by mass of the solid content (non-volatile content) in the epoxy resin composition, it is preferably 0.1 parts by mass to 2 parts by mass, and in the case of using an organophosphorus compound, it is also preferably formulated in the range of 0.1 to 10 parts by mass, particularly preferably in the range of 0.5 to 6 parts by mass .

Moreover, when a phosphorus compound is used as a flame retardant, hydrotalcite, magnesium hydroxide, a boron compound, zirconium oxide, calcium carbonate, zinc molybdate, etc. can also be used together as a flame retardant aid, for example.

In the present invention, it is preferable to use a phosphorus compound as the flame retardant, but the flame retardants described below may also be used.

Examples of nitrogen-based flame retardants include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenthiazine, and are preferably triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds. The compounding 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 the degree of desired flame retardancy, such as the solid content in the epoxy resin composition (Non-volatile matter) 100 mass parts, It is preferable to mix|blend in the range of 0.05-10 mass parts, It is especially preferable to mix|blend in the range of 0.1-5 mass parts. In addition, when using a nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

As the silicone-based flame retardant, any organic compound containing a silicon atom can be used without particular limitation, and examples thereof include silicone oil, silicone rubber, and silicone resin, but are not limited thereto. The blending amount of the 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 the degree of desired flame retardancy. For example, in the epoxy resin composition, It is preferable to mix|blend in the range of 0.05 mass part - 20 mass parts in 100 mass parts of solid content (non-volatile matter). In addition, when a silicone-based 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, low-melting glass, and the like. 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 the degree of desired flame retardancy, for example, when the epoxy resin, epoxy resin It is preferably formulated in the range of 0.05 to 20 parts by mass in 100 parts by mass of the solid content (non-volatile content) in the epoxy resin composition, including curing agents, flame retardants, other fillers, and additives. , It is particularly preferable to prepare it within the range of 0.5 parts by mass to 15 parts by mass.

Examples of organic metal salt-based flame retardants include ferrocene, metal acetylacetonate complexes, organic metal carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, metal atoms and aromatic compounds or heterocyclic compounds. Compounds formed by ion bonding or coordination bonding, etc., but are 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 the degree of desired flame retardancy. In 100 parts by mass of the solid content (non-volatile content) of the entire epoxy resin composition, such as hardeners for epoxy resins, flame retardants, and other fillers or additives, it is preferably 0.005 parts by mass to 10 parts by mass deployment within the scope.

In the epoxy resin composition, fillers, thermoplastic resins, or thermosetting resins other than epoxy resins, silane coupling agents, antioxidants, mold release agents, and defoamers can be formulated as needed within the range that does not impair the properties. , emulsifier, thixotropy imparting agent, lubricant, pigment and other additives.

Examples of fillers 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, aramid fibers, and ceramic fibers, or microparticle rubber. Among these fillers, those that are not decomposed or dissolved by acidic compounds such as permanganate aqueous solution used in the surface roughening treatment of hardened products are preferred, and in particular, fused silica or crystalline silica is easy to obtain fine particles. The particles are therefore preferred. Moreover, when making the compounding quantity of a filler especially large, it is preferable to use fused silica. Fused silica can be used in either crushed or spherical form, but it is more preferable to mainly use spherical fused silica in order to increase the compounding amount of fused silica and suppress an increase in the melt viscosity of the molding material. Furthermore, in order to increase the compounding quantity of spherical silica, it is preferable to adjust the particle size distribution of spherical silica suitably. In addition, the filler may be treated with a silane coupling agent or an organic acid such as stearic acid. Generally, the reasons for using fillers include the effect of improving the impact resistance of the cured product and the reduction in linear expansion of the cured product. In addition, when metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide are used, they function as flame retardant aids to improve flame retardancy. When used for applications such as conductive paste, conductive fillers such as silver powder or copper powder can be used.

In consideration of low linear expansion or flame retardancy of the cured product, it is preferable that the compounding amount of the filler is high. Preferably it is 1 mass % - 90 mass % with respect to the solid content (non-volatile content) in an epoxy resin composition, More preferably, it is 5 mass % - 80 mass %, More preferably, it is 10 mass % - 60 mass % . If the compounding amount is large, there is a possibility that the adhesiveness required for the laminated board application will decrease, and furthermore, there may be a possibility that the cured product becomes brittle and cannot obtain sufficient mechanical properties. Moreover, if the compounding amount is small, there exists a possibility that the impact resistance of hardened|cured material may improve, etc., and it is not the compounding effect of a filler.

In addition, the average particle diameter of the inorganic filler is preferably 0.05 μm to 1.5 μm, more preferably 0.1 μm to 1 μm. When the average particle diameter of an inorganic filler is this range, the fluidity|fluidity of an epoxy resin composition will be maintained favorably. In addition, the average particle diameter can be measured using a particle size distribution measuring device.

Blending a thermoplastic resin is particularly effective when molding an epoxy resin composition into a sheet form or a film form. Examples of thermoplastic resins include phenoxy resins, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, and polyvinyl acetate resins. Ester resin, polymethyl methacrylate resin, polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin , polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyethersulfone resin, polysulfone resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formaldehyde resin, etc., but 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 such as phenol resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, diallyl phthalate resins, and thermosetting polyimides. Thermosetting resins, organic pigments such as quinacridone, azo, and phthalocyanine, or inorganic pigments such as titanium oxide, metal foil pigments, and antirust pigments, or hindered amines, benzotriazoles, UV absorbers such as benzophenone series, or antioxidants such as hindered phenol series, phosphorus series, sulfur series, and hydrazide series, or coupling agents such as silane series and titanium series, or stearic acid, palmitic acid, stearic acid Release agents such as zinc and calcium stearate, additives such as leveling agents, rheology control agents, pigment dispersants, shrinkage inhibitors, defoamers, etc. It is preferable that the compounding quantity of these other additives is the range of 0.01 mass % - 20 mass % with respect to the solid content (non-volatile content) in an epoxy resin composition.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. Furthermore, the hardened|cured material of this invention can be obtained easily by hardening by the method similar to a conventionally well-known method. As a method for obtaining a cured product, the same method as a known epoxy resin composition can be used, and casting, injection, pouring, dipping, drop coating, transfer molding, compression molding, etc. can be preferably used, or A method such as forming a resin sheet, copper foil with resin, prepreg, etc., laminating them, heating and pressing and hardening 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 molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films.

Examples of applications using the epoxy resin composition include materials for circuit boards, sealing materials, casting materials, conductive pastes, adhesives, and the like. Examples of materials for circuit boards include prepregs, resin sheets, metal foils with resin, resin compositions for printed wiring boards or flexible wiring boards, and interlayer insulating materials for build-up boards. Insulating materials, adhesive films for build-up, resist inks, etc. Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up can be used to embed passive parts such as capacitors or active parts such as integrated circuit (IC) chips. It is used as an insulating material for so-called substrates for embedding electronic components in substrates. Among these applications, in terms of properties such as high flame retardancy, high heat resistance, low dielectric properties, and solvent solubility, it is preferred as a printed wiring board material, a resin composition for a flexible wiring board, and a build-up substrate. Used for circuit board (laminate) materials such as interlayer insulating materials and semiconductor sealing materials.

When the epoxy resin composition is made into a plate shape such as a laminated board, the filler to be used is preferably a fibrous filler, more preferably glass, in terms of dimensional stability, bending strength, and the like. Cloth, fiberglass mat, glass roving.

By impregnating an epoxy resin composition into a fibrous reinforcing base material, it can be set as a prepreg used for a printed wiring board or the like. As the fibrous reinforcing base material, inorganic fibers such as glass, or woven or non-woven fabrics of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, and aramid resin can be used. , but not limited to this.

The method of producing the prepreg from the epoxy resin composition is not particularly limited, and it can be obtained, for example, by preparing a varnish-like epoxy resin composition containing the organic solvent and further adjusting the organic solvent to an appropriate The resin varnish of viscosity is impregnated into the fibrous substrate, and then heat-dried to semi-harden the resin component (B-staged). The heating temperature is preferably from 50°C to 200°C, more preferably from 100°C to 170°C, depending on the type of organic solvent to be used. The heating time is adjusted according to the type of organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, more preferably 3 minutes to 20 minutes. At this time, the mass ratio of the epoxy resin composition to be used and the reinforcing base material is not particularly limited, but usually it is 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 form or a film form and used. In this case, it can be formed into a sheet or a film using a conventionally known method. The method for producing the resin sheet is not particularly limited, and it can be obtained, for example, by using a reverse roll coater, a chipped wheel coater, a molded film, etc. on a supporting base film that does not dissolve in the resin varnish. The resin varnish is coated with a coater such as a coater, and then heat-dried to B-stage the resin component. In addition, an adhesive sheet having release layers on both surfaces of the adhesive layer is obtained by laminating another supporting base film as a protective film on the coated surface (adhesive layer) as necessary, followed by drying.

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, polyester film, etc. An imide film and the like, among these supporting base films, a polyethylene terephthalate film having excellent dimensional accuracy without cracks and other defects and excellent cost is preferable. Moreover, it is preferable that it is a metal foil which facilitates multilayering of a laminated board, especially copper foil. 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 and hardly causes lamination failure.

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 adhesive sheet, it is preferable to perform surface treatment with a release agent in advance. In addition, the thickness of the coating resin varnish is preferably 5 μm to 200 μm, more preferably 5 μm to 100 μm, in terms of thickness after drying. The heating temperature is preferably from 50°C to 200°C, more preferably from 100°C to 170°C, depending on the type of organic solvent to be used. The heating time is adjusted according to the type of organic solvent used or the curability of the prepreg, and is preferably 1 minute to 40 minutes, more preferably 3 minutes to 20 minutes.

The resin sheet obtained in this way usually becomes an insulating adhesive sheet having insulating properties, but it is also possible to obtain conductive adhesive by mixing conductive metal or metal-coated fine particles in the epoxy resin composition. piece. In addition, the support base film is peeled off after being laminated on the circuit board, or heat-cured to form an insulating layer. If the supporting base film is peeled off after heating and hardening the adhesive sheet, it is possible to prevent dust and the like from adhering during the hardening step. Here, the insulating adhesive sheet is also an insulating sheet.

The resin-attached metal foil obtained using the epoxy resin composition will be described. As the metal foil, copper, aluminum, brass, nickel, or the like alone, alloy, or composite metal foil can be used. It is preferable to use a metal foil having a thickness of 9 μm to 70 μm. The method of manufacturing the resin-coated metal foil from a flame-retardant resin composition containing a phosphorus-containing epoxy resin and a metal foil is not particularly limited. For example, it can be obtained by using a roll coater or the like on a A resin varnish obtained by adjusting the viscosity of an epoxy resin composition with a solvent is coated on one side of the metal foil, and then heat-dried to semi-cure the resin component (B-staged) to form a resin layer. When the resin component is semi-hardened, it can heat-dry at 100 degreeC - 200 degreeC for 1 minute - 40 minutes, for example. Here, it is desirable that the thickness of the resin portion of the metal foil with resin is 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, However, It is not limited to this. For example, in the case of using prepregs to form a laminate, one or more prepregs are laminated, metal foil is placed on one or both sides to form a laminate, and the laminate is pressurized and heated, thereby The prepreg is hardened and integrated to obtain a laminated board. Here, as the metal foil, copper, aluminum, brass, nickel, or the like alone, alloy, or composite metal foil can be used.

As the conditions for heating and pressing the laminate, it is enough to adjust the heating and pressing under the condition that the epoxy resin composition is hardened, but if the pressure of the pressing is too low, there will be defects in the obtained laminated board. Bubbles remain inside and electrical characteristics deteriorate, so it is ideal to pressurize under conditions that satisfy moldability. The heating temperature is preferably 160°C to 250°C, more preferably 170°C to 220°C. The applied pressure is preferably 0.5 MPa to 10 MPa, more preferably 1 MPa to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if the heating temperature is high, the cured product may be thermally decomposed. If the applied pressure is low, air bubbles may remain inside the obtained laminated sheet, and the electrical characteristics may be lowered. If the applied pressure is high, the resin may flow before curing, and there is a possibility that a laminated sheet having a desired thickness may not be obtained. In addition, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if the heating and pressing time is long, there may be a possibility of thermal decomposition of the cured product.

Furthermore, the single-layer laminated board obtained in this way can be used as an inner layer material to make a multilayer board. In this case, first, a circuit is formed on the laminate by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution to blacken the surface to obtain an inner layer material. On the circuit forming surface of one or both sides of the inner layer, an insulating layer is formed by using a prepreg or resin sheet, an insulating adhesive sheet, or metal foil with resin, and a conductive layer is formed on the surface of the insulating layer. , thus forming a multilayer board.

In addition, when forming an insulating layer using a prepreg, one or a plurality of prepregs are placed on the circuit formation surface of the inner layer material, and a metal foil is further placed on the outside to form a laminate. Then, the laminate is integrally molded with heat and pressure, thereby forming a cured product of the prepreg as an insulating layer, and forming a metal foil on the outer side thereof as a conductor layer. Here, as the metal foil, the same metal foil as that used in the laminate used as the inner layer material can be used. In addition, heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. A printed wiring board can be molded by further forming via holes or forming circuits on the surface of the multilayer laminate molded as described above by an additive method or a subtractive method. In addition, by repeating the above process as an inner layer material with this printed wiring board, a multi-layer multilayer board can be further formed.

For example, when forming an insulating layer using an insulating adhesive sheet, the insulating adhesive sheet is arranged on the circuit formation surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is disposed between the circuit-forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is integrally molded under heat and pressure to form a cured product of the insulating adhesive sheet as an insulating layer, and multilayering of the inner layer material is formed. Alternatively, a cured product of the insulating adhesive sheet is formed between the inner layer material and the metal foil as the conductor layer as the insulating layer. Here, as the metal foil, the same metal foil as that used in the laminate used as the inner layer material can be used. In addition, heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.

In addition, when coating an epoxy resin composition on a laminate to form an insulating layer, the epoxy resin composition is coated to a thickness of preferably 5 μm to 100 μm, and then heated at 100° C. to 200° C., preferably 150° C. Heat-drying is performed at -200 degreeC for 1 minute - 120 minutes, Preferably it is 30 minutes - 90 minutes, and it is formed into a sheet shape. It is generally formed by a method called a casting method. Desirably, the thickness after drying is 5 μm to 150 μm, preferably 5 μm to 80 μm. In addition, the viscosity of the epoxy resin composition is preferably in the range of 10 mPa·s to 40000 mPa·s at 25° C., more preferably 200 mPa·s in order to obtain a sufficient film thickness and hardly cause uneven coating or streaks. ~30000mPa·s. On the surface of the multilayer laminate thus formed, via holes or circuits are further formed by an additive method or a subtractive method to form a printed wiring board. In addition, by repeating the above process as an inner layer material with this printed wiring board, it is possible to further form a multilayer laminated board.

The sealing materials obtained by using the epoxy resin composition of the present invention are for tape-shaped semiconductor chips, for potting liquid sealing, for underfill, for semiconductor interlayer insulating films, and the like, and can be preferably used among them. For example, as semiconductor encapsulation molding, the method of casting an epoxy resin composition, or molding an epoxy resin composition using a transfer molding machine, an injection molding machine, etc., and heating at 50°C to 200°C for 2 hours to 10 hours to obtain a molded product.

In order to prepare the epoxy resin composition as a semiconductor sealing material, the following method can be enumerated: pre-mixing in the epoxy resin composition an optional preparation such as an inorganic filler, or additives such as a coupling agent and a mold release agent, Then, it is sufficiently melt-mixed using an extruder, a kneader, a roll, or the like until it becomes uniform. In this case, silica is usually used as the inorganic filler, and in this case, it is preferable to mix the inorganic filler in a ratio of 70% by mass to 95% by mass in the epoxy resin composition.

In the case of using the epoxy resin composition obtained in the above manner as a tape-like sealant, the following method can be cited: heat it to make a semi-hardened sheet, and after making a sealant tape, the sealant The adhesive tape is placed on the semiconductor chip, heated to 100°C to 150°C to soften it for molding, and 170°C to 250°C to completely harden it. Moreover, when using as a potting type liquid sealing material, what is necessary is just to apply|coat to a semiconductor chip or an electronic component after dissolving the obtained epoxy resin composition in a solvent as needed, and to harden it as it is.

In addition, the epoxy resin composition of the present invention can be further used as a resist ink. In this case, the following method can be cited: blending a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a hardening agent in an epoxy resin composition, and further adding pigments, talc, and fillers to produce After forming a composition for resist ink, it is applied on a printed substrate by screen printing, and then a cured product of resist ink is produced. The curing temperature at this time is preferably in a temperature range of about 20°C to 250°C.

The epoxy resin composition of the present invention was prepared and cured by heating and curing to evaluate the cured product. As a result, a cured product exhibiting unprecedented low dielectric properties and having an excellent balance of heat resistance, adhesiveness, and the like was obtained. In addition, by blending a flame retardant, low dielectric properties can also be exhibited, and flame retardancy can be imparted without deteriorating heat resistance, adhesiveness, and the like.

[Example]

Although an Example and a comparative example were given and this invention was demonstrated concretely, this invention is not limited to these examples unless the summary is exceeded. Unless otherwise specified, a part means a mass part, and % means a mass %.

Analysis methods and measurement methods are shown below.

(1) Epoxy equivalent: according to the Japanese Industrial Standard (JIS) K7236 specification.

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

(3) Glass transition temperature: According to the IPC-TM-650 2.4.25.c specification, using a differential scanning calorimetry device (manufactured by Hitachi High-Tech Co., Ltd., EXSTAR6000 DSC6200) under the heating condition of 20°C/min The DSC·Tgm (intermediate temperature of the variation curve with respect to the tangent line between the glass state and the rubber state) at the time of measurement is expressed.

(4) Copper foil peeling strength and interlayer adhesive force: It measured based on JIS C6481 standard, and interlayer adhesive force measured by peeling between the 7th layer and the 8th layer.

(5) Relative permittivity and dielectric loss tangent: According to the IPC-TM-650 2.5.5.9 specification, use a material analyzer (manufactured by Agilent Technologies) to obtain the permittivity at a frequency of 1 GHz using the capacitance method and dielectric loss tangent.

(6) Flame retardancy: evaluated by the vertical method according to UL94. Evaluations are marked with V-0, V-1, V-2.

Synthesis Example 1

In the separable flask made of glass with a stirring device, a thermometer, a nitrogen gas introduction device, a condenser tube and a dropping device, 100 parts of TX-1468 (the epoxy resin represented by the formula (5) of the new day Manufactured by Tetsuzumikin Chemical Co., Ltd., epoxy equivalent is 219), 0.11 part of tetramethylammonium iodide, while nitrogen gas is injected, the temperature is raised, and the temperature is maintained at 120° C. for 30 minutes to remove moisture in the system. Next, while maintaining the reaction temperature of 130°C to 140°C, 11.5 parts of diphenylmethane diisocyanate (NCO concentration: 34%) was added dropwise over 3 hours while heating to 60°C. Stirring was continued for 60 minutes after completion|finish of dripping, maintaining the same temperature, and the epoxy resin (resin 1) containing an oxazolidone ring was obtained. The obtained resin 1 had an oxazolidinone ring modification rate (Rox) of 0.2, an epoxy equivalent of 300, and a softening point of 85°C.

Synthesis example 2

100 parts of TX-1468 and 0.12 parts of tetramethylammonium iodide were placed in the same apparatus as in Synthesis Example 1, and the temperature was raised while injecting nitrogen gas. The temperature was maintained at 120° C. for 30 minutes to remove moisture in the system. Next, while maintaining a reaction temperature of 140°C to 150°C, toluene diisocyanate (a mixture of 2,4-toluene diisocyanate (80%) and 2,6-toluene diisocyanate (20%), NCO Concentration is 48%) 17.8 parts. Stirring was continued for 60 minutes after completion|finish of dripping, maintaining the same temperature, and the epoxy resin (resin 2) containing an oxazolidone ring was obtained. The obtained resin 2 had a modification rate (Rox) of 0.45, an epoxy equivalent of 464, and a softening point of 125°C.

Synthesis example 3

100 parts of TX-1468 and 0.12 parts of tetramethylammonium iodide were placed in the same apparatus as in Synthesis Example 1, and the temperature was raised while injecting nitrogen gas. The temperature was maintained at 120° C. for 30 minutes to remove moisture in the system. 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. Stirring was continued for 60 minutes after completion|finish of dripping, maintaining the same temperature, and the epoxy resin (resin 3) containing an oxazolidone ring was obtained. The obtained resin 3 had a modification rate (Rox) of 0.36, an epoxy equivalent of 400, and a softening point of 115°C.

In addition, the content rate (mass %) of the unreacted epoxy resin was 49% for the resin 1, 20% for the resin 2, and 33% for the resin 3.

Synthesis Example 4

91 parts of 4,4'-(4-methylcyclohexylene)bisphenol, 358 parts of epichlorohydrin, 4 parts of ion-exchanged water were charged into the same device as Synthetic Example 1, and the temperature was raised to 50 while stirring. ℃. After uniform dissolution, 5.3 parts of 49% sodium hydroxide aqueous solution was charged and reacted for 3 hours. Next, after raising the temperature to 64°C, the pressure was reduced to such an extent that water reflux occurred, and 48 parts of 49% sodium hydroxide aqueous solution was added dropwise over 3 hours. During the dropwise addition, the distilled water and epichlorohydrin were separated by reflux in a separation tank. , the epichlorohydrin was returned to the reaction vessel, water was removed from the system, and the reaction was performed. After completion of the reaction, the temperature was increased to 70°C to perform dehydration, and the temperature was set to 135°C to collect remaining epichlorohydrin. Return to normal pressure, add and dissolve 204 parts of methyl isobutyl ketone (Methyl isobutyl ketone, MIBK). 127 parts of ion-exchanged water was added, stirred and left still to dissolve and remove by-produced common salt in water. Next, 2.9 parts of 49% sodium hydroxide aqueous solution was charged, and it stirred and reacted at 80 degreeC for 90 minutes, and purified reaction was performed. MIBK was added and washed with water several times to remove ionic impurities. The solvent is recovered to obtain the epoxy resin (c4) in which X of the formula ( ¹ ) is 4-methylcyclohexylene, R is H, and ⁿ is 0.05. The epoxy equivalent of the obtained epoxy resin (c4) was 206.

Next, 100 parts of the obtained epoxy resin (c4) and 0.12 parts of tetramethylammonium iodide were loaded into the same device as in Synthesis Example 1, and the temperature was raised while injecting nitrogen gas, and the temperature was maintained at 120° C. for 30 minutes. And remove the moisture in the system. Next, 12.2 parts of diphenylmethane diisocyanates were dripped over 3 hours, heating to 60 degreeC, maintaining the reaction temperature of 130 degreeC - 140 degreeC. Stirring was continued for 60 minutes after completion|finish of dripping, maintaining the same temperature, and the epoxy resin (resin 4) containing an oxazolidone ring was obtained. The obtained resin 4 had a modification rate (Rox) of 0.2, an epoxy equivalent of 290, and a softening point of 80°C.

Synthesis Example 5

86.5 parts of 4,4'-cyclohexylenebisphenol, 358 parts of epichlorohydrin, and 4 parts of ion-exchanged water were charged to the same apparatus as Synthesis Example 1, and it heated up to 50 degreeC, stirring. After uniform dissolution, 5.3 parts of 49% sodium hydroxide aqueous solution was charged and reacted for 3 hours. Next, after raising the temperature to 64°C, the pressure was reduced to such an extent that water reflux occurred, and 48 parts of 49% sodium hydroxide aqueous solution was added dropwise over 3 hours. During the dropwise addition, the distilled water and epichlorohydrin were separated by reflux in a separation tank. , the epichlorohydrin was returned to the reaction vessel, water was removed from the system, and the reaction was performed. After completion of the reaction, the temperature was increased to 70°C to perform dehydration, and the temperature was set to 135°C to collect remaining epichlorohydrin. It returned to normal pressure, and 204 parts of MIBK was added and dissolved. 127 parts of ion-exchanged water was added, stirred and left still to dissolve and remove by-produced common salt in water. Next, 2.9 parts of 49% sodium hydroxide aqueous solution was charged, and it stirred and reacted at 80 degreeC for 90 minutes, and purified reaction was performed. MIBK was added and washed with water several times to remove ionic impurities. The solvent is recovered to obtain an epoxy resin (c5). The epoxy resin (c5) is an epoxy resin in which X of the formula ( ¹ ) is ⁴ -cyclohexylene, R is H, and n is 0.06, and the epoxy equivalent is 200.

Next, 100 parts of the obtained epoxy resin (c5) and 0.11 parts of tetramethylammonium iodide were loaded into the same device as in Synthesis Example 1, and the temperature was raised while injecting nitrogen gas, and the temperature was maintained at 120° C. for 30 minutes. And remove the moisture in the system. Next, 12.5 parts of diphenylmethane diisocyanates were dripped over 3 hours, heating to 60 degreeC, maintaining the reaction temperature of 130 degreeC - 140 degreeC. After completion of the dropwise addition, stirring was continued for 60 minutes while maintaining the same temperature to obtain an oxazolidone ring-containing epoxy resin (resin H1). The obtained resin H1 had a modification rate (Rox) of 0.2, an epoxy equivalent of 285, and a softening point of 85°C.

Synthesis Example 6

105 parts of phenol novolak (hydroxyl equivalent: 105, softening point: 130°C) and 0.1 part of p-toluenesulfonic acid were charged to the same apparatus as in Synthesis Example 1, and the temperature was raised to 150°C. While maintaining the same temperature, 94 parts of styrene were dripped over 3 hours, and stirring was continued at the same temperature for 1 hour further. Then, 500 parts of MIBK was added and the content was dissolved, and it washed with water five times at 80 degreeC. Next, MIBK was distilled off under reduced pressure to obtain a styrene-modified novolac phenol compound (APN-A). The obtained APN-A had a phenolic hydroxyl equivalent of 199 and a softening point of 110°C. In the formula (3), the average number of substitutions of 1-phenylethyl groups with respect to one A ¹ is 0.9.

Synthesis Example 7

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

Synthesis Example 8

To the same device as Synthesis Example 1, 210 parts of 1-naphthol aralkyl resins (manufactured by Nippon Steel Sumitomo Metal Co., Ltd., SN-475, phenolic hydroxyl equivalent of 210, and softening point of 77° C.), 0.18 Parts of p-toluenesulfonic acid, the temperature was raised to 150°C. While maintaining the same temperature, 135 parts of styrene were dripped over 3 hours, and stirring was continued at the same temperature for 1 hour further. Then, the same treatment as in Synthesis Example 6 was performed to obtain a styrene-modified novolac phenol compound (APN-C). The obtained APN-C had a phenolic hydroxyl equivalent of 345 and a softening point of 88°C. The average number of substitutions of ¹ -phenylethyl groups relative to one A was 1.3.

Synthesis Example 9

500 parts of phenol and 190 parts of boron trifluoride ether complex were charged into the same apparatus as in Synthesis Example 1, and the temperature was raised to 120°C. While maintaining the same temperature, 176 parts of dicyclopentadiene was dripped over 6 hours, and reaction was performed at 130 degreeC for 4 hours further. Then, neutralization and phenol recovery are performed. Furthermore, 500 parts of MIBK was added and the content was dissolved, and it washed with water four times at 80 degreeC. Then, MIBK was distilled off under reduced pressure to obtain a dicyclopentadiene/phenol co-condensation resin.

Next, 196 parts of the obtained dicyclopentadiene/phenol co-condensation resin and 0.11 parts of p-toluenesulfonic acid were charged to 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 were dripped over 3 hours, and stirring was continued at the same temperature for 1 hour further. Then, the same treatment as in Synthesis Example 6 was performed to obtain a substituent-containing novolac phenol compound (APN-D). The obtained APN-D had a phenolic hydroxyl equivalent of 228 and a softening point of 122°C. The average number of substitutions of ¹ -phenylethyl relative to one A is 0.3.

Synthesis Example 10

500 parts of phenol and 9.5 parts of boron trifluoride ether complex were placed in the same apparatus as in Synthesis Example 1, and the temperature was raised to 120°C. While maintaining the same temperature, 88 parts of dicyclopentadiene was dripped over 6 hours, and reaction was performed at 130 degreeC for 4 hours further. Then, neutralization and phenol recovery are performed. Furthermore, 300 parts of MIBK was added and the content was melt|dissolved, and it washed with water four times at 80 degreeC. Then, MIBK was distilled off under reduced pressure to obtain a dicyclopentadiene/phenol co-condensation resin.

Next, 178 parts of the obtained dicyclopentadiene/phenol co-condensation resin and 0.11 parts of p-toluenesulfonic acid were charged to 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 were dripped 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 substituent-containing novolac phenol compound (APN-E). The obtained APN-E had a phenolic hydroxyl equivalent of 205 and a softening point of 90°C. The average number of substitutions of benzyl groups relative to ^one A1 is 0.3.

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

(epoxy resin)

(1) Epoxy resin containing oxazolidinone ring (a)

Resin 1-Resin 4: Epoxy resins obtained in Synthesis Example 1-Synthesis Example 4

(2) Other epoxy resins

Resin H1: the epoxy resin obtained in Synthesis Example 5

TX-1468: described

YDPN-638: Phenol novolak type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Albert (Epotohto) YDPN-638, epoxy equivalent is 176)

KDCP-130: dicyclopentadiene type 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: 155)

BisP-MC: 4,4'-(4-methylcyclohexylene) bisphenol (reagent, phenolic hydroxyl equivalent)

(2) Novolac phenol compound (b2)

APN-A to APN-E: Novolac phenol compounds obtained in Synthesis Example 6 to Synthesis Example 10

(3) Other hardeners

PN: Phenol novolac resin (manufactured by Showa Denko Co., Ltd., Shonol BRG-557, phenolic hydroxyl equivalent: 105, softening point: 80°C)

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

DCPD: dicyclopentadiene phenol compound (manufactured by Qunying Chemical Co., Ltd., GDP9140, phenolic hydroxyl equivalent: 196, softening point: 130° C.)

(hardening accelerator)

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

(flame retardant)

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

Example 1

Prepare 100 parts of resin 1 as an epoxy resin, 29.0 parts of BisP-TMC as a hardener, 29.0 parts of APN-A, and 0.2 parts of 2E4MZ as a hardening accelerator, and dissolve them in MEK, propylene glycol monomethyl ether , N,N-dimethylformamide adjusted in the mixed solvent to obtain an epoxy resin composition varnish.

The obtained epoxy resin composition varnish is impregnated in the glass cloth in the hot air circulation oven of 150 ℃ to the impregnated glass cloth

The obtained epoxy resin composition varnish was impregnated in glass cloth (ISO7628 type, thickness 0.16 mm). The impregnated glass cloth was dried in a hot air circulation oven at 150° C. to obtain a prepreg. Eight pieces of the obtained prepregs were stacked up and down with copper foil (manufactured by Mitsui Metal Mining Co., Ltd., 3EC-III, with a thickness of 35 μm), and subjected to 2MPa under the temperature conditions of 130°C x 15 minutes + 190°C x 80 minutes. Vacuum pressing to obtain a 1.6 mm thick laminate. Table 1 shows the results of the glass transition temperature, copper foil peel strength, and interlayer adhesive force of the laminate.

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

Embodiment 2 to Embodiment 8

It prepared with the preparation quantity (part) of Table 1, and performed the same operation using the apparatus similar to Example 1, and obtained the laminated board and the test piece. The same test as in Example 1 was performed, and the results are shown in Table 1. In addition, "b1/b2 (equivalent ratio)" in a table shows the equivalent ratio (molar ratio) of a bisphenol compound (b1) and a novolac phenol compound (b2). In addition, in all the examples and comparative examples, the equivalent ratio (molar ratio) of the epoxy resin (A) to the curing agent (B) was 1.0.

Comparative example 1 to comparative example 7

It prepared with the preparation quantity (part) of Table 2, and performed the same operation using the apparatus similar to Example 1, and obtained the laminated board and the test piece. The same test as in Example 1 was performed, and the results are shown in Table 2.

[Table 1]

Example 1 2 3 4 5 6 7 8 Resin 1 100 100 100 100 100 100 100 100 BisP-TMC 29.0 6.4 47.5 32.4 35.6 30.7 29.4 - BisP-MC - - - - - - - 27.5 APN-A 29.0 58.0 5.3 - - - - 27.5 APN-B - - - 32.4 - - - - APN-C - - - - 35.6 - - - APN-D - - - - - 30.7 - - APN-E - - - - - - 29.4 - 2E4MZ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 b1/b2 (equivalent ratio) 56/44 12/88 92/8 63/34 69/31 60/40 57/43 59/41 Glass transition temperature (°C) 182 180 183 175 165 186 188 175 Copper foil peel strength (kN/m) 1.6 1.4 1.8 1.6 1.6 1.4 1.4 1.6 Interlayer adhesion (kN/m) 1.5 1.1 2.1 1.5 1.5 1.4 1.4 1.7 Relative permittivity 2.9 2.9 2.8 2.8 2.9 2.9 2.8 2.9 Dielectric loss tangent 0.012 0.011 0.013 0.010 0.011 0.013 0.012 0.013

[Table 2]

comparative example 1 2 3 4 5 6 7 Resin 1 100 100 100 100 100 100 100 BisP-TMC 51.6 - - - - 20.8 28.8 BisP-MC - 47.0 - - - - - APN-A - - 66.3 - 26.7 - - APN-D - - - 75.9 - - - Bis-Z - - - - 26.7 - - PN - - - - - 20.8 - DCPD - - - - - - 28.8 2E4MZ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Glass transition temperature (°C) 184 155 178 188 165 185 186 Copper foil peel strength (kN/m) 1.6 1.8 1.3 1.4 1.6 1.7 1.6 Interlayer adhesion (kN/m) 2.2 2.1 0.7 1.2 1.6 1.7 1.8 Relative permittivity 2.9 2.9 2.9 3.0 2.9 3.0 3.0 Dielectric loss tangent 0.015 0.016 0.011 0.015 0.013 0.016 0.016

Embodiment 9～Example 12 and Comparative Example 8～Comparative Example 10

It prepared with the preparation quantity (part) of Table 3, and performed the same operation using the apparatus similar to Example 1, and obtained the laminated board and the test piece. The same test as in Example 1 was performed, and the results are shown in Table 3.

[table 3]

Example 13 to Example 16 and Comparative Example 11

It prepared with the preparation quantity (part) of Table 4, and performed the same operation using the apparatus similar to Example 1, and obtained the laminated board and the test piece. The flame retardant was prepared in such an amount that the phosphorus content of the epoxy resin composition became 2.5%. The same test as in Example 1 was performed, and the results are shown in Table 4. In addition, the test piece for flame retardancy measurement was produced by etching both surfaces of the laminated board, and the flame retardancy test was performed using the test piece, and the result is shown in Table 4.

[Table 4]

[industrial availability]

The epoxy resin composition of the present invention and its cured product are excellent in heat resistance, adhesiveness, and dielectric properties, and can be used as an epoxy resin composition for applications such as cured epoxy resin, prepreg, and laminated board. In addition, the epoxy resin composition further compounded with a flame retardant and its cured product are excellent in flame retardancy, heat resistance, adhesiveness, and dielectric properties, and can be used as electronic circuits that meet the recent demands for higher functionality. Epoxy resin composition for high functional materials such as substrate materials.

Claims (6)

1. an epoxy resin composition, it contains epoxy resin (A) and curing agent (B), and the feature of described epoxy resin composition is: epoxy resin (A) contains by following formula (1) The epoxy resin (a) containing an oxazolidone ring obtained by expressing the epoxy resin (c) and the isocyanate compound (d), and the hardener (B) contains a bisphenol compound represented by the following formula (2) (b1) and a novolac phenol compound (b2) represented by the following formula (3), In the formula, X ¹ represents a cycloalkylene group with 5 to 8 ring members having at least one hydrocarbon group with 1 to 20 carbons as a substituent; R ¹ independently represents a hydrogen atom, a halogen atom, a hydrogen atom with 1 to 20 carbons, Halogenated hydrocarbon group, or a hydrocarbon group with a carbon number of 1 to 20 that may have heteroatoms; G represents glycidyl; n represents the number of repetitions, and the average value is 0 to 5; In the formula, X ² represents a cycloalkylene group with 5 to 8 ring members having at least one hydrocarbon group with 1 to 20 carbons as a substituent; R ² independently represents a hydrogen atom, a halogen atom, and a hydrocarbon group with 1 to 20 carbons. Halogenated hydrocarbon groups, or hydrocarbon groups with 1 to 20 carbon atoms that may have heteroatoms; In the formula, A ¹ each independently represent an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic ring groups may also have a hydrocarbon group with a carbon number of 1 to 49 that may have a heteroatom as a substitute group, with an average of 0.1 to 2.5 selected from aryl groups with 6 to 48 carbons, aryloxy groups with 6 to 48 carbons, aralkyl groups with 7 to 49 carbons, and aralkyloxy groups with 7 to 49 carbons Substituents in the group; T represents any one 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 above; In the formula, R ³ and R ⁴ independently represent a hydrogen atom or a hydrocarbon group with 1 to 20 carbons that may have heteroatoms; R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group with 1 to 6 carbons; 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 that may have a heteroatom as a substituent. 2. The epoxy resin composition according to claim 1, characterized in that: the mass ratio of the bisphenol compound (b1) to the novolac phenol compound (b2) is in the range of 5/95 to 95/5 . 3. The epoxy resin composition according to claim 1 or 2, characterized in that: the bisphenol compound (b1) is 4,4'-(3,3,5-trimethylcyclohexylene)bis Phenol or 4,4'-(3,3,5,5-tetramethylcyclohexylene)bisphenol. 4. epoxy resin composition according to claim 1 and 2 is characterized in that: described novolac phenolic compound (b2) is the phenolic compound represented by following formula (4), In the formula, R ⁷ independently represents a hydrocarbon group with 1 to 6 carbons, and R ⁸ is a substituent represented by the following formula (4a); p is 0.1 to 2.5 on average, and q is a number of 0 to 2, p+q is 0.1～3 on average; 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 carbons. 5. according to claim 1 and 2 described epoxy resin compositions, it is characterized in that: relative to the epoxy group 1 mole of described epoxy resin (A), the active hydrogen group of described curing agent (B) is 0.2 mole to 1.5 mole. 6. A hardened epoxy resin, characterized in that: it is formed by hardening the epoxy resin composition according to any one of claims 1 to 5.