JP2019052278A - Epoxy resin, epoxy resin composition, cured product, and laminate for electric-electronic circuit - Google Patents

Abstract

To provide an epoxy resin having low solution viscosity while maintaining excellent heat resistance and dielectric properties of a polyphenylene ether skeleton.SOLUTION: A linear epoxy resin has two or more of a bisphenol structure (between aromatic rings, there is a group selected from a direct bond, a C1-13 divalent hydrocarbon group, -O-, -S-, -SO-, -C(CF)-, and -CO-) and a structure selected from C1-13 divalent hydrocarbon groups, and a structure represented by the following formula (16), and includes a glycidyl group at both terminals (Y is a structure including a bisphenol structure; p is an average of the number of repetitions and is 0-30).SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin having excellent heat resistance and having reduced viscosity when made into a solution. The present invention also relates to an epoxy resin composition containing the epoxy resin and a curing agent, a cured product thereof, and a laminate for an electric / electronic circuit comprising the epoxy resin composition.

  Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, and electrical properties, so they can be used in various fields such as adhesives, paints, civil engineering and building materials, and insulating materials for electrical and electronic parts. It is used. In particular, in the electric / electronic field, it is widely used in insulating casting, laminated materials, sealing materials and the like.

  In recent years, in the field of electrical and electronic equipment, the miniaturization, weight reduction, and high functionality of the equipment have progressed, and printed wiring boards used for electrical and electronic equipment, especially multilayer printed wiring boards, have higher multilayers. There is a demand for improvement in the size, density, thickness, weight, and reliability and molding processability. Along with the progress of miniaturization of wiring, further high heat resistance is required as a characteristic for the resin side as a substrate material. Further, in order to increase the signal transmission speed and reduce the loss during signal transmission, it is required that the dielectric constant and dielectric loss tangent are low.

  Patent Document 1 discloses a specific polyphenylene ether oligomer having a relatively low molecular weight as an oligomer-modified epoxy resin that gives a cured product having moisture resistance, low dielectric constant, and low dielectric loss tangent without impairing heat resistance, adhesion, and workability. An oligomer-modified epoxy resin obtained by a reaction between an epoxy resin and an epoxy resin has been proposed.

JP 2004-256717 A

  The epoxy resin described in Patent Document 1 is obtained by a reaction between a relatively low-molecular polyphenylene ether oligomer and an epoxy resin, and has high heat resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) due to the effect of polyphenylene ether. A cured product with excellent resistance can be obtained. However, as a result of investigations by the present inventors, it has been found that the inclusion of a polyphenylene ether skeleton makes the epoxy resin have a high viscosity when made into a solution and insufficient handling properties. Since the epoxy resin is often handled as a solution at the time of manufacturing a printed wiring board, a high solution viscosity has a great adverse effect on the manufacturing process.

  An object of the present invention is to solve the above problems and to use an epoxy resin and an epoxy resin composition having a low solution viscosity while maintaining the excellent heat resistance and dielectric properties of the polyphenylene ether skeleton, and using this epoxy resin composition. Another object of the present invention is to provide a cured product and a laminate for an electric / electronic circuit.

  As a result of intensive studies to solve the above problems, the present inventors have introduced a chemical structure as a third component into the polyphenylene ether-modified epoxy resin, so that the solution viscosity is low, and the heat resistance and dielectric properties are excellent. It was found that an epoxy resin was obtained. That is, the gist of the present invention resides in the following [1] to [17].

[1] An epoxy resin represented by the following formula (1).

(In the formula (1), A represents a structure selected from the group represented by the structure represented by the formula (2) and a divalent hydrocarbon group having 1 to 13 carbon atoms (hereinafter referred to as “structure (A-1)”). 2) and a structure represented by the formula (3), and R ¹ and R ² are both groups represented by the formula (5), or one of the groups represented by the formula ( 5) and the other is a hydrogen atom, R ³ is a hydrogen atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group, m is an average value of the number of repetitions, And represents a number of 0 to 500. In formula (2), X represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ -, and a group selected from ^-CO-, R 4 ^{to R 11} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, carbon atoms -12 is a group selected from an alkoxy group having 6 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, and an alkynyl group having 1 to 12 carbon atoms. 4), wherein R ^{12 to} R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. , An alkenyl group having 1 to 12 carbon atoms, and an alkynyl group having 1 to 12 carbon atoms, p and q are average values of the number of repetitions, and each independently represents a number of 0 to 30. In formula (4), Z represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —CO—. from a group ^selected, R 29 ^{to R 36} each independently represent a hydrogen atom, It is a group selected from an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, and an alkynyl group having 1 to 12 carbon atoms. .)

[2] The epoxy resin according to [1], wherein A in the formula (1) contains 60 to 90 mol% of the structure (A-1).

[3] The epoxy resin according to [1] or [2], wherein the structure (A-1) includes one or more of the structures represented by the following formulas (6) to (15).

[4] The epoxy resin according to any one of [1] to [3], wherein the structure represented by the formula (3) includes a structure represented by the following formula (16).

(In Formula (16), Y, p, and q are synonymous with Y, p, and q in Formula (3), respectively.)

[5] An epoxy resin that is a reaction product of a bifunctional epoxy resin represented by the following formula (17), a compound represented by the following formula (18), and a compound represented by the following formula (19).

(In Formula (17) and Formula (18), A ′ is a structure selected from the group represented by Formula (2) ′ and a divalent hydrocarbon group having 1 to 13 carbon atoms (hereinafter, “ 2 or more of the structure (A′-1) ”), n is an average of the number of repetitions, and represents an integer of 0 to 6. In Formula (18), R ′ ³ is hydrogen. An atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group, wherein X ′ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—. , —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —CO—, wherein R ′ ^{4 to} R ′ ¹¹ are each independently a hydrogen atom, a carbon number of 1 to 12 alkyl groups, C1-C12 alkoxy groups, C6-C12 aryl groups, C1-C12 alkenyl groups, and C1-C12 Is a group selected from an alkynyl group in. The formula (19), Y 'has the formula (4)' include a structure represented by, R ^'12 to R' ²⁷ are each independently a hydrogen atom, C 1 -C A group selected from an -12 alkyl group, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, and an alkynyl group having 1 to 12 carbon atoms; ^'28 is a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms or an aromatic carbonyl group,, p', q 'is an average number of repetitions, each independently, represent a number of 0 to 30 In formula (4) ′, Z ′ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and a group selected from -CO-, R ^'29 ~R' ³⁶ are each independently a hydrogen atom, the number of carbon atoms 12 alkyl group, an alkoxy group having 1 to 12 carbon atoms, a group selected from aryl group, an alkenyl group having 1 to 12 carbon atoms, and alkynyl group having 1 to 12 carbon atoms having 6 to 12 carbon atoms.)

[6] The amount of the compound represented by formula (18) is the sum of the bifunctional epoxy resin represented by formula (17), the compound represented by formula (18), and the compound represented by formula (19). The epoxy resin according to [5], which is 3 to 20 mol% with respect to the number of moles.

[7] The epoxy according to [5] or [6], wherein the structure (A′-1) includes one or more of the structures represented by the following formulas (6) ′ to (15) ′: resin.

[8] The epoxy resin according to any one of [5] to [7], wherein the compound represented by the formula (19) includes a compound represented by the following formula (20).

(In Formula (20), Y ', p', and q 'have the same meanings as Y', p ', and q' in Formula (19).)

[9] The epoxy resin according to any one of [1] to [8], which has a weight average molecular weight of 2,000 to 50,000.

[10] The epoxy resin according to any one of [1] to [9], wherein the epoxy equivalent is 400 g / equivalent to 15,000 g / equivalent.

[11] An epoxy resin composition comprising the epoxy resin of the present invention according to any one of [1] to [10] and a curing agent.

[12] The epoxy resin composition according to [11], including 0.1 to 100 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy resin of the present invention.

[13] Further, other epoxy resins other than the epoxy resin of the present invention are included, and 1 to 99 parts by weight of the other epoxy resins are included in a total of 100 parts by weight of the epoxy resin of the present invention and other epoxy resins as a solid content. [11] or [12] The epoxy resin composition described in [12].

[14] The epoxy resin composition according to [13], including 0.1 to 100 parts by weight of a curing agent with respect to a total of 100 parts by weight of the epoxy resin of the present invention and another epoxy resin.

[15] The curing agent according to [11] to [14], wherein the curing agent is at least one selected from the group consisting of phenolic curing agents, amide curing agents, imidazoles, active ester curing agents, and cyanate ester curing agents. The epoxy resin composition in any one.

[16] A laminate for an electric / electronic circuit, comprising the epoxy resin composition according to any one of [11] to [15].

[17] A cured product obtained by curing the epoxy resin composition according to any one of [11] to [15].

According to the present invention, it is possible to provide an epoxy resin having a low solution viscosity while maintaining the excellent heat resistance and dielectric properties of the polyphenylene ether skeleton. Moreover, the epoxy resin composition using this epoxy resin can provide a cured product excellent in dielectric properties and heat resistance with good handling properties, workability, and productivity.
For this reason, the epoxy resin and epoxy resin composition of the present invention can be applied to various fields such as adhesives, paints, building materials for civil engineering, insulating materials for electric / electronic parts, etc., especially in the electric / electronic field. Useful as casting, laminating material, sealing material and the like.
The epoxy resin of the present invention and the epoxy resin composition containing the same are used for multilayer printed wiring boards, laminates for electric / electronic circuits such as capacitors, adhesives such as film adhesives and liquid adhesives, semiconductor sealing materials, It can be suitably used for fill materials, 3D-LSI interchip fills, insulating sheets, prepregs, heat dissipation substrates, and the like.

Embodiments of the present invention will be described in detail below. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following descriptions unless it exceeds the gist. It is not something. In addition, when using the expression “to” in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.
In this specification, the carbon number of each substituent refers to the total number of carbon atoms including the substituent when the substituent further has a substituent.
In the present specification, the compound having the structure of the above formula (3) and the generic name of the structure itself are referred to as polyphenylene ether, but may be generally referred to as polyphenylene oxide, polyaryl ether, or the like.

〔Epoxy resin〕
The epoxy resin of the present invention is represented by the following formula (1).

(In the formula (1), A represents a structure selected from the group represented by the structure represented by the formula (2) and a divalent hydrocarbon group having 1 to 13 carbon atoms (hereinafter referred to as “structure (A-1)”). Two or more of the above and a structure represented by the formula (3),
R ¹ and R ² are both a group represented by the formula (5), or one is a group represented by the formula (5) and the other is a hydrogen atom,
R ³ is a hydrogen atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group,
m is an average value of the number of repetitions and represents a number of 0 to 500.
In formula (2), X represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —CO—. A group selected from
R ^{4 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, And a group selected from alkynyl groups having 1 to 12 carbon atoms.
In formula (3), Y includes the structure represented by formula (4),
R ^{12 to} R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, And a group selected from an alkynyl group having 1 to 12 carbon atoms,
p and q are average values of the number of repetitions, and each independently represents a number of 0 to 30.
In formula (4), Z represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —CO—. A group selected from
R ^{29 to} R ³⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, And a group selected from alkynyl groups having 1 to 12 carbon atoms. )

  The epoxy resin of the present invention is characterized by excellent heat resistance and dielectric properties and low solution viscosity. In the above formula (1), by having a polyphenylene ether skeleton, excellent heat resistance and low dielectric properties can be obtained, and as the structure (A-1), other structures other than two or more polyphenylene ether skeletons can be appropriately used. By having it, the solution viscosity which is a subject can be reduced.

[Chemical structure]
In the formula (1), A is a structure selected from the group represented by the structure represented by the formula (2) and a divalent hydrocarbon group having 1 to 13 carbon atoms (hereinafter “structure (A-1)”). And a structure represented by the formula (3) (hereinafter sometimes referred to as “structure (3)”).

Examples of the divalent hydrocarbon group having 1 to 13 carbon atoms in the structure (A-1) include a linear, branched or cyclic alkylene group, an arylene group, and a group in which two or more of these are combined. The following can be mentioned. In the following, “Ph” represents a phenyl group.
For example, a group represented by — (CH ₂ ) _k —, such as —CH ₂ —, —C ₂ H ₄ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CH (Ph) _{-, - C (CH 3)} Ph -, - CPh 2 -, 9,9- fluorenylene group, 1,1-cyclopropylene group, 1,1-cyclobutylene group, 1,1-cyclopentylene group, 1, 1-cyclohexylene group, 3,3,5-trimethyl-1,1-cyclohexylene group, 1,1-cyclododecylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,2-cyclo Pentylene group, 1,2-cyclohexylene group, 1,2-phenylene group, 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,3-cyclohexylene group, 1,3-phenylene group 1,4-cyclohexylene group, 1,4-phen Ren group, a 2,2-dimethylpropylene and the like.

Among these, the divalent hydrocarbon group having 1 to 13 carbon atoms in the structure (A-1) is — (CH ₂ ) _k — () from the viewpoint of easy availability of raw materials and low solution viscosity. k is 2 to 12), 2,2-dimethylpropylene group, -CH (Ph)-, 9,9-fluorenylene group, 1,1-cyclohexylene group, 3,3,5-trimethyl-1,1-cyclohex A silene group and a 1,1-cyclododecylene group are preferable, and in particular, — (CH ₂ ) _k — (k is 2 to 12, particularly preferably any of k = 2, 4, 6, 12), 2,2-dimethylpropylene. Groups are preferred.

In the formula (2), X is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ — and —CO—. Is a group selected from

Here, the following are mentioned as a C1-C13 bivalent hydrocarbon group in X of said Formula (2).
For example, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —CH (Ph) —, —C (CH ₃ ) Ph—, —CPh ₂ —, 9,9-fluorenylene. Group, 1,1-cyclopropylene group, 1,1-cyclobutylene group, 1,1-cyclopentylene group, 1,1-cyclohexylene group, 3,3,5-trimethyl-1,1-cyclohexylene group 1,1-cyclododecylene group, 1,2-ethylene group, 1,2-cyclopropylene group, 1,2-cyclobutylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group, 1, 2-phenylene group, 1,3-propylene group, 1,3-cyclobutylene group, 1,3-cyclopentylene group, 1,3-cyclohexylene group, 1,3-phenylene group, 1,4-butylene group 1,4-cyclohexylene group, 1 4-phenylene group.

Among these, since the one where the degree of freedom of rotation of the two benzene rings in the formula (2) is lower tends to be excellent in heat resistance, X is a direct bond, —CH ₂ —, —CH (CH ₃ ) —, — _{C (CH 3) 2 -,} - C (CF 3) 2 -, - CH (Ph) -, - C (CH 3) Ph -, - CPh 2 -, 9,9- fluorenylene group, 1,1-cyclohexylene Two benzenes such as silene group, 3,3,5-trimethyl-1,1-cyclohexylene group, 1,1-cyclododecylene group, —O—, —S—, —SO ₂ —, —CO—, etc. Those having 0 or 1 atoms involved in ring connection are preferred. Among these, a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C (CH ₃ ) Ph—, 9,9-fluorenylene group, 3, 3, 5 - trimethyl-1,1-cyclohexylene group, more preferably 1,1-cyclododecylene group, a direct _{bond, -C (CH 3) Ph -} , - C (CF 3) 2 -, 9,9- fluorenylene group, 3 , 3,5-trimethyl-1,1-cyclohexylene group and 1,1-cyclododecylene group are more preferable.

When X is a direct bond, the biphenyl skeleton in the formula (2) is a 2,2′-biphenyl skeleton, a 2,3′-biphenyl skeleton, a 2,4′-biphenyl skeleton, or a 3,3′-biphenyl. Any of a skeleton, a 3,4′-biphenyl skeleton, and a 4,4′-biphenyl skeleton may be used, but a 4,4′-biphenyl skeleton is preferable.
On the other hand, X represents —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —CH (Ph) —, —C (CH ₃ ) Ph—. , -CPh ₂ -, 9,9- fluorenylene group, 1,1-cyclohexylene group, 3,3,5-trimethyl-1,1-cyclohexylene group, 1,1-cyclododecylene group, -O -, - S In the case of —, —SO ₂ —, —CO—, etc., the bonding positions on the benzene ring in the formula (2) are 2,2′-position, 2,3′-position, 2,4′-position, 3 , 3′-position, 3,4′-position, and 4,4′-position, but preferably 4,4′-position.

In the formula (2), R ^{4 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a carbon number. It is a group arbitrarily selected from an alkenyl group having 1 to 12 carbon atoms and an alkynyl group having 1 to 12 carbon atoms.

Here, the alkyl group having 1 to 12 carbon atoms of R ^{4 to} R ¹¹ in the formula (2) may be linear, branched or cyclic, and has a substituent such as a phenyl group. The following may be mentioned.
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, methylcyclohexyl group, n-octyl group, cyclooctyl group, n-nonyl group, 3,3,5-trimethylcyclohexyl group, n- Decyl group, cyclodecyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, naphthylmethyl group, phenethyl group, 2-phenylisopropyl group, etc. .

Moreover, as a C1-C12 alkoxy group of R < ⁴ > -R < ¹¹ > in the said Formula (2), any may be linear, branched, and cyclic, and it has substituents, such as a phenyl group. The following may be mentioned.
For example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, isopentoxy group, neopentoxy group, tert-pentoxy group, cyclopent Toxyl group, n-hexyloxy group, isohexyloxy group, cyclohexyloxy group, n-heptoxy group, cycloheptoxy group, methylcyclohexyloxy group, n-octyloxy group, cyclooctyloxy group, n-nonyloxy group, 3,3,5-trimethyl Cyclohexyloxy group, n-decyloxy group, cyclodecyloxy group, n-undecyloxy group, n-dodecyloxy group, cyclododecyloxy group, benzyloxy group, methylbenzyloxy group, dimethyl benzyloxy group, trimethylbenzyloxy group, naphthylmethoxy Group, Enechirokishi group, 2-phenyl-iso-propoxy group.

Examples of the aryl group having 6 to 12 carbon atoms of R ^{4 to} R ¹¹ in the formula (2) include the following.
For example, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, styryl group, xylyl group, n-propylphenyl group, isopropylphenyl group, mesityl group, ethynylphenyl group, naphthyl group, Examples thereof include a phenyl group and a naphthyl group, which may have a substituent such as an alkyl group, such as a vinyl naphthyl group.

The alkenyl group having 2 to 12 carbon atoms of R ^{4 to} R ¹¹ in the formula (2) may be linear, branched or cyclic, and has a substituent such as a phenyl group. The following are examples.
For example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylvinyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, cyclohexenyl group, cyclohexadienyl Group, cinnamyl group, naphthyl vinyl group and the like.

The alkynyl group having 2 to 12 carbon atoms of R ^{4 to} R ¹¹ in the formula (2) may be linear, branched or cyclic, and has a substituent such as a phenyl group. The following are examples.
Examples include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,3-butanedienyl group, phenylethynyl group, naphthylethynyl group and the like.

Among the examples mentioned above, R ^{4 to} R ^{11 in the} formula (2) are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group. This is because if the substituent is too sterically large, aggregation between molecules is hindered and heat resistance may be reduced.
R ^{4 to} R ¹¹ are each an alkyl group having 1 to 12 carbon atoms other than a hydrogen atom, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or carbon. In the case of an alkynyl group having 1 to 12, the number of substituents other than a hydrogen atom in the formula (2) is preferably 2 or 4, and when the number of substituents is 2, the substituent is 2- It is preferred that the substituent is in the position and 2′-position, and when the number of substitution is 4, the substituent is preferably in the 2-position, 2′-position, 6-position and 6′-position.

  The epoxy resin of the present invention is particularly a group consisting of the structure (A-1) in the formula (1), that is, the structure represented by the formula (2) and a divalent hydrocarbon group having 1 to 13 carbon atoms. It is preferable that the structure selected from 1 includes at least one structure selected from the following formulas (6) to (15) from the viewpoint of improving heat resistance and reducing the solution viscosity.

  In particular, the structure (A-1) preferably contains two or more structures selected from the above formulas (6) to (15), and in particular, selected from the above formulas (6) and (8) to (15). It is preferable that two or more types of structures are included, and further, a combination of the above formulas (6) and (8), a combination of the above formulas (6) and (9), and a combination of the above formulas (6) and (10). A combination of the above formulas (6) and (11), a combination of the above formulas (6) and (12), a combination of the above formulas (6) and (13), and the above formulas (6) and (14). ), The above formula (8) and the formula (9), the above formula (8) and the formula (10), the above formula (8) and the formula (11), the above formula (8) and the formula The combination of (12), the above formula (8) and the formula (13), the above formula (8) and the formula (14) A combination of the above formula (9) and the formula (10), a combination of the above formula (9) and the formula (11), a combination of the above formula (9) and the formula (12), the above formula (9) and the formula ( 13), the above formula (9) and the formula (14), the above formula (10) and the formula (11), the above formula (10) and the formula (12), the above formula (10) and It is particularly preferable that two or more of the structures (A-1) are included in combination of Formula (13) and the combination of Formula (10) and Formula (14).

  In the structure represented by the formula (3) included in A in the formula (1), Y includes the structure represented by the formula (4).

Z in the formula (4) is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —CO. -Is a group selected from-, and specific examples thereof include those similar to X in the formula (2), and preferred ones are also the same.
Further, in the above formula ^{(4), R} 29 ~R ³⁶ independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, A group selected from an alkenyl group having 1 to 12 carbon atoms and an alkynyl group having 1 to 12 carbon atoms, and specific examples thereof include those similar to those in R ^{4 to} R ¹¹ in the formula (2). The preferred ones are the same, including the number of substituents and substitution positions.

Moreover, in said formula (3), R < ¹² > -R < ²⁷ > is respectively independently a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C6-C12 aryl group, A group selected from an alkenyl group having 1 to 12 carbon atoms and an alkynyl group having 1 to 12 carbon atoms, and specific examples thereof include those similar to those in R ^{4 to} R ¹¹ in the formula (2). The preferred ones are the same, including the number of substituents and substitution positions.

  Note that Y in the formula (3) may include a structure other than the structure represented by the formula (4), but in 100 mol% of Y, the structure represented by the formula (4) is 50. It is preferably contained in an amount of at least mol%, particularly 80 to 100 mol% from the viewpoint of improving heat resistance and dielectric properties.

  As the structure (3) represented by the formula (3), for example, a structure including a structure represented by the following formula (16) is preferable.

(In Formula (16), Y, p, and q are synonymous with Y, p, and q in Formula (3), respectively.)

  In said Formula (3), p and q are the number of repetitions, and are average values. p and q are independent of each other, and the range of the values is 0 or more from the viewpoint of improving heat resistance and dielectric properties, and 30 or less from the viewpoint of the handleability of the resin. From the viewpoint of further improving heat resistance and dielectric properties, p and q are preferably 1 or more, and more preferably 3 or more. On the other hand, from the viewpoint of further improving the handleability of the resin, p and q are preferably 20 or less, more preferably 10 or less. The numbers of p and q can be calculated from the number average molecular weight Mn obtained by the gel permeation chromatography method (GPC method). Specific examples of the GPC method will be described later in Examples.

In the formula (1), R ¹ and R ² may be the same or different from each other, and are a hydrogen atom or a chemical structure represented by the formula (5), and at least one of them is the formula (5). It is a group represented.

Wherein in formula (1), R ³ is any one of a hydrogen atom, an aliphatic group having 1 to 10 carbon atoms or an aromatic group.

Examples of the aliphatic carbonyl group having 1 to 10 carbon atoms of R ³ in the formula (1) include an acetyl group, a propanoyl group, an isopropanoyl group, a butanoyl group, an isobutanoyl group, a sec-butanoyl group, a tert-butanoyl group, and pentanoyl. Group, isopentanoyl group, hexanoyl group, heptanoyl group, cyclohexylcarbonyl group, octanoyl group, decanoyl group, acetoacetyl group, phenylpropanoyl group, cinnamyl group and the like. Among them, those having 2 to 4 carbon atoms are more preferable, and specifically, an acetyl group, a propanoyl group, a butanoyl group, and an acetoacetyl group are preferable.

The aromatic carbonyl group of R ³ in the formula (1) is preferably an aromatic carbonyl group having 6 to 10 carbon atoms, and examples thereof include a benzoyl group, a methylbenzoyl group, a methoxybenzoyl group, and a furylcarbonyl group. Groups are preferred.

  The epoxy resin of the present invention is usually a mixture of molecules having different terminals, substituents, repeating numbers p, q, etc., and molecules having different repeating numbers m described below.

  In said Formula (1), m is a repeating number and is an average value. The range of the value is 0 or more from the viewpoint of improving heat resistance, and is 500 or less from the viewpoint of the handleability of the resin. From the viewpoint of further improving the heat resistance, m is preferably 0.5 or more, more preferably 1 or more, while from the viewpoint of further improving the handleability of the resin, it is preferably 100 or less. Yes, more preferably 50 or less, still more preferably 20 or less. The m number can be calculated from the number average molecular weight Mn obtained by the gel permeation chromatography method (GPC method). Specific examples of the GPC method will be described later in Examples.

  The epoxy resin of this invention is a group which consists of a structure represented by Formula (2) and a C1-C13 bivalent hydrocarbon group as A in said Formula (1) from a viewpoint of reducing a solution viscosity. 2 or more types of structures (A-1) which are structures selected from are included. Since the structure (A-1) is derived from the structure of the raw material used at the time of production, the case where two or more structures (A-1) are contained in one molecule and the case where each structure is contained in a separate molecule. It may also be a mixture of inclusions.

  From the viewpoint of reducing the solution viscosity, the total amount of the structure (A-1) contained as A in the formula (1) is 50 mol% or more with respect to 100 mol% of A. It is preferable that it is contained, more preferably 55 mol% or more, and particularly preferably 60 mol% or more. Further, from the viewpoint of maintaining good heat resistance and dielectric properties, it is preferably 95 mol% or less, more preferably 92 mol% or less, and particularly preferably 90 mol% or less. Each content can be calculated from the raw material charge ratio at the time of production.

  From the viewpoint of improving the solution viscosity, the epoxy resin of the present invention has a content of any one of two or more structures (A-1) contained as A in the formula (1). It is preferable that it is 1 mol% or more with respect to 100 mol% of this, More preferably, it is preferable to contain 3 mol% or more. Further, from the viewpoint of maintaining good heat resistance and dielectric properties, it is preferably 50 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less.

  In addition, the epoxy resin of the present invention balances solution viscosity, heat resistance, and dielectric properties, so that the molar ratio between the structure (A-1) and the structure (3) ([number of moles of structure (A-1)] / [Number of moles of structure (3)]) is preferably 10/90 or more, more preferably 30/70 or more, further preferably 50/50 or more, and 60/40 or more. It is particularly preferred. On the other hand, from the viewpoint of heat resistance and dielectric properties, it is preferably 99/1 or less, more preferably 90/10 or less, and even more preferably 85/15 or less.

  In addition, although A in Formula (1) may contain structures other than a structure (A-1) and a structure (3), the solution viscosity by containing a structure (A-1) and a structure (3). From the viewpoint of heat resistance and dielectric properties, the total content of the structure (A-1) and the structure (3) in A100 mol% is preferably 50 mol% or more, particularly preferably 80 to 100 mol%.

[Weight average molecular weight (Mw)]
The weight average molecular weight (Mw) of the epoxy resin of the present invention is preferably 2,000 to 50,000. When the weight average molecular weight is lower than 2,000, the heat resistance and dielectric properties are low, and when it is higher than 50,000, it becomes difficult to handle the resin. The weight average molecular weight (Mw) of the epoxy resin of the present invention is more preferably 3,000 or more, further preferably 5,000 or more, from the viewpoint of further improving heat resistance and dielectric properties, while having good handleability. In view of the above, 30,000 or less is more preferable, and 20,000 or less is more preferable. In addition, the weight average molecular weight and number average molecular weight of an epoxy resin can be measured by the above-mentioned gel permeation chromatography method (GPC method).

[Epoxy equivalent]
The epoxy equivalent of the epoxy resin of the present invention is preferably 400 to 15,000 g / equivalent. The epoxy equivalent of the epoxy resin of the present invention is preferably 420 g / equivalent or more, more preferably 430 g / equivalent or more, from the viewpoint of further improving heat resistance and dielectric properties. On the other hand, from the viewpoint of maintaining good curability, it is preferably 12,000 g / equivalent or less, and more preferably 10,000 g / equivalent or less. Furthermore, it is preferable that an epoxy equivalent is below a number average molecular weight. Since the epoxy equivalent is the molecular weight per epoxy group, the epoxy equivalent being equal to or less than the number average molecular weight means that one or more epoxy groups are contained per molecule on average. Thereby, the epoxy resin of the present invention itself participates in the curing reaction and can be incorporated into the crosslinked structure.

[Method for producing epoxy resin]
The epoxy resin of the present invention is obtained, for example, by reacting a bifunctional epoxy resin represented by the following formula (17), a compound represented by the following formula (18), and a compound represented by the following formula (19). can get. That is, the epoxy resin of the present invention is a reaction product of a bifunctional epoxy resin represented by the following formula (17), a compound represented by the following formula (18), and a compound represented by the following formula (19). It is.

(In Formula (17) and Formula (18), A ′ is a structure selected from the group represented by Formula (2) ′ and a divalent hydrocarbon group having 1 to 13 carbon atoms (hereinafter, “ Including two or more of structure (A′-1) ”,
n is an average value of the number of repetitions and represents an integer of 0 to 6.
In Formula (18), R ′ ³ is a hydrogen atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group.
In formula (2) ′, X ′ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and — A group selected from CO-
R ′ ^{4 to} R ′ ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 1 to 12 carbon atoms. A group selected from a group and an alkynyl group having 1 to 12 carbon atoms.
In Formula (19), Y ′ includes a structure represented by Formula (4) ′,
R ′ ^{12 to} R ′ ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 1 to 12 carbon atoms. A group selected from a group and an alkynyl group having 1 to 12 carbon atoms,
R ′ ²⁸ is a hydrogen atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group,
p ′ and q ′ are average values of the number of repetitions, and each independently represents a number of 0 to 30.
In formula (4) ′, Z ′ represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and — A group selected from CO-
R ′ ^{29 to} R ′ ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 1 to 12 carbon atoms. A group selected from a group and an alkynyl group having 1 to 12 carbon atoms. )

As the structure (A′-1) of A ′ in the above formulas (17) and (18), the same structure as the structure (A-1) can be mentioned, and the preferable ones are also the same. That is, X ′ and R ′ ^{4 to} R ′ ¹¹ in the formula (2) ′ have the same meanings as X and R ^{4 to} R ¹¹ in the formula (2), respectively.
Moreover, as the hydrogen atom of R ′ ³ in the above formula (18), the aliphatic carbonyl group having 1 to 10 carbon atoms, or the aromatic carbonyl group, those similar to R ³ in the above formula (1) can be mentioned.
Y ′ in the above formula (19) is the same as Y in the above formula (3), and the preferred ones are also the same. That is, Z ′ and R ′ ^{29 to} R ′ ³⁶ in the above formula (4) ′ have the same meanings as Z and R ^{29 to} R ³⁶ in the above formula (4), respectively.
Also, R ^'12 ~R' ²⁷ in formula (19), the formula (3) is the same as ^R 12 ^{to R 27} in, preferable ones are also same. Further, p ′ and q ′ in the above formula (19) are the same as p and q in the above formula (3), and preferable ones are also the same.

Things as the bifunctional epoxy resin represented by the formula used in the production of the epoxy resin (17) of the present invention, for example, the formula (18) bisphenol-based compound represented by the (R ^'3 is a hydrogen atom ) With an epihalohydrin by a known method.

Moreover, when using a diester compound as a compound represented by the said Formula (18) or a compound represented by the said Formula (19) for manufacture of the epoxy resin of this invention, the said diester compound is the said Formula (18), for example. ) (R ^'3 is as a hydrogen atom) and / or the formula (19) (dihydroxy compound R ^'28 is represented by a one) hydrogen atom, an acid chloride or acid anhydride, or carboxylic acid And can be obtained by acylation by a condensation reaction.

  The structure (A′-1) in A ′ of the formula (17) and / or the formula (18) includes at least one of structures represented by the following formulas (6) ′ to (15) ′. In order to reduce the solution viscosity of the resulting epoxy resin, it is preferable.

  Usually, the bifunctional epoxy resin represented by the formula (17) includes at least one of the structures (A′-1), and the compound represented by the formula (18) is represented by the formula (17). And at least one structure (A′-1) different from the structure (A′-1) included in the bifunctional epoxy resin.

N in the formula (17) is an average value of the number of repetitions, and is a number of 0 or more and 6 or less. Reaction of bisphenol compound with an epihalohydrin of the formula (18) (R ^'3 is as a hydrogen atom) in a known manner, the equation that n is greater than 0 in (17) is generally. In order to set n to 0, an epoxy resin produced by a known method is highly purified by a technique such as distillation and crystallization, or after allylation of the bisphenol compound represented by the formula (18). There is a method of epoxidizing by oxidizing the olefin part. Further, for example, when finely adjusting the adhesiveness to metal, by using an appropriate number n of epoxy resins, in the epoxy resin of the present invention within a range that does not significantly affect other physical properties such as hygroscopicity. An appropriate amount of secondary hydroxyl groups can be present.

In the formula (19), Y ′ includes the formula (4) ′. The detailed description of the formula (4) ′ is the same as the description of the formula (4) included as Y in the formula (3). In other words, detailed description of the 'Z' in formula (4) is the same as the description of Z in Formula (4), detailed description of the R ^'29 ~R ^'36 is similar to the description of ^R 29 ^{to R 36} is there.
In the formula (19), p ′ and q ′ are each independently a number from 0 to 30. The detailed description of p ′ and q ′ is the same as the above description of p and q in the formula (3).
In the formula (19), R ′ ^{12 to} R ′ ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, It is a group arbitrarily selected from a C 1-12 alkenyl group and a C 1-12 alkynyl group. The detailed description of R ′ ^{12 to} R ′ ^{27 is the same as} the description of R ^{12 to} R ^{27 in} the formula (3).

In the formula (19), R ^'28 is hydrogen atom, an aliphatic group having 1 to 10 carbon atoms or an aromatic group. The detailed description of R ′ ^{28 is the same as} the description of R ³ in the formula (1).

  The compound represented by the formula (19) is preferably a compound having a polystyrene-equivalent number average molecular weight of 500 to 8,000 measured by a gel permeation chromatography method (GPC method). That is, from the viewpoint of maintaining good heat resistance and dielectric properties, the number average molecular weight of this compound is preferably 500 or more, and more preferably 1,000 or more. Moreover, from a viewpoint of ensuring handleability and keeping solution viscosity and melt viscosity low, 8,000 or less is preferable, 5,500 or less is more preferable, and 3,000 or less is particularly preferable.

  The compound represented by the formula (19) preferably includes, for example, a compound represented by the following formula (20).

(In Formula (20), Y ', p', and q 'have the same meanings as Y', p ', and q' in Formula (19).)

The method for producing the compound represented by the formula (19) is not particularly limited. For example, (i) a method using an enzyme catalyst, (ii) a method using a radical initiator, (iii) a method using a complex catalyst, etc. There is. In the method (i), a dihydric phenol compound is produced by polymerization together with a monohydric phenol compound in the presence of an enzyme catalyst. (Ii) The method is described in U.S. Pat. Nos. 3,367,978 and 4,234,706, and White et al. "White_et_
al. "J. Org. Chem. 1969, Vol. 34, 297-303. Describes the method. Specifically, it is a method in which polyphenylene ether (number average molecular weight 10,000 to 30,000) obtained industrially is redistributed in the presence of a polyphenol compound and a radical initiator. The polyphenol compound to be used may be any polyfunctional phenol having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, biphenols, phenol novolac, Examples include cresol novolac. Examples of the radical initiator include benzoyl peroxide, dicumyl peroxide, tert-butylperoxyneodecanoate, tert-butylcumyl peroxide, lauroyl peroxide, and the like. As the method (iii), a known method described in JP-A-49-69797 can be used. It is a method for selectively obtaining a polyphenylene ether oligomer having a phenolic hydroxyl group at a polymer terminal by oxidative copolymerization of a 2,6-substituted phenol and a phenol compound having two phenolic hydroxyl groups in one molecule. It is. Specifically, it can be obtained by oxidative polymerization of 2,6-xylenol and a dihydric phenol compound in a solvent such as benzene, toluene, chloroform and the like using a copper-pyridine complex catalyst in the presence of oxygen.

  The amount of the compound represented by the formula (18) used for the production of the epoxy resin of the present invention is the bifunctional epoxy resin represented by the formula (17), the compound represented by the formula (18) and the formula From the viewpoint of reducing the solution viscosity with respect to the total number of moles of the compound represented by (19), it is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol%. That's it. Moreover, from a viewpoint of keeping heat resistance and a dielectric characteristic favorable, Preferably it is 50 mol% or less, More preferably, it is 30 mol% or less, More preferably, it is 20 mol% or less.

  Moreover, the ratio of the compound represented by the said Formula (18) used for manufacture of the epoxy resin of this invention and the compound represented by the said (19) can take arbitrary molar ratios of 1 / 99-99 / 1. However, in order to balance the dielectric properties and heat resistance with the solution viscosity, the molar ratio ([number of moles of compound represented by formula (18)] / [mol of chemical structure represented by formula (19)] The number]) is more preferably 5/95 or more, further preferably 10/90 or more, particularly preferably 15/85 or more, and preferably 80/20 or less, It is more preferably 70/30 or less, further preferably 60/40 or less, and particularly preferably 55/45 or less.

  In the production of the epoxy resin of the present invention, the above-mentioned bifunctional epoxy resin (bifunctional epoxy resin represented by the above formula (17)), diester compound and / or dihydroxy compound (expressed by the above formula (18)). The amount used of the compound and the compound represented by the formula (19)) is the compounding equivalent ratio of (epoxy group): ((ester group) and / or (phenolic hydroxyl group)) = 1-4. It is preferable to use so that it may become 5: 1. It is preferable for this equivalent ratio to be in the above-mentioned range since the reaction can easily proceed with an epoxy group at the molecular end.

  A catalyst may be used for the synthesis of the epoxy resin of the present invention, and any catalyst may be used as long as it has a catalytic ability to promote a reaction between an epoxy group and a hydroxyl group and / or an ester group. Good. For example, tertiary amines, cyclic amines, imidazoles, organic phosphorus compounds, quaternary ammonium salts and the like can be mentioned.

  Specific examples of the tertiary amine include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine, pyridine, 4- (dimethylamino) pyridine and the like.

  Specific examples of cyclic amines include 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0. ] Nonene-5 etc. are mentioned.

  Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

  Specific examples of the organophosphorus compound include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tris (p-tolyl) phosphine, tricyclohexylphosphine, tri (tert-butyl) phosphine, tris (p -Methoxyphenyl) phosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, tetrabutylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetra Phenylphosphonium bromide, triphenylmethylphosphonium Amide, triphenylmethyl phosphonium iodide, triphenyl ethyl phosphonium chloride, triphenyl ethyl phosphonium bromide, triphenyl ethyl phosphonium iodide, triphenyl benzyl phosphonium chloride, triphenyl benzyl phosphonium bromide, and the like.

  Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride, etc. And the like.

  Among the catalysts listed above, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0] nonene-5, 2-ethyl-4-methylimidazole, tris (p-tolyl) phosphine, tricyclohexylphosphine, tri (tert-butyl) phosphine, tris (p-methoxyphenyl) phosphine, tetra Methylammonium hydroxide is preferred, especially 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0] nonene-5, 2- Ethyl-4-methylimidazole and tetramethylammonium hydroxide are preferred. Moreover, a catalyst can use only 1 type and can also be used in combination of 2 or more type.

  The amount of the catalyst used is usually 0.001 to 1% by weight in the reaction solids, but when these compounds are used as a catalyst, they remain as catalyst residues in the resulting epoxy resin, and the printed wiring board The content of nitrogen derived from the catalyst in the resulting epoxy resin is preferably 2000 ppm or less because there is a risk of deteriorating the insulating properties or shortening the pot life of the composition. The content is preferably used so that it is preferably 2000 ppm or less, particularly the content of nitrogen derived from the catalyst in the obtained epoxy resin is 1000 ppm or less, and the content of phosphorus derived from the catalyst in the epoxy resin is 1000 ppm or less. It is preferable to use so that it becomes.

  The epoxy resin of the present invention may use a reaction solvent in the step of the synthesis reaction at the time of production, and any solvent may be used as long as it dissolves the epoxy resin. Examples include aromatic solvents, ketone solvents, amide solvents, glycol ether solvents, and the like. The solvent may be used alone or in combination of two or more.

  Specific examples of the aromatic solvent include benzene, toluene, xylene and the like. Specific examples of the ketone solvent include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, dioxane and the like.

  Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.

  Specific examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples include mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like.

  The solid concentration in the synthesis reaction during the production of the epoxy resin is preferably 35 to 95% by weight. Further, when a highly viscous product is produced during the reaction, the reaction can be continued by adding an additional solvent. After completion of the reaction, the solvent can be removed or further added as necessary.

  In the production of an epoxy resin, a polymerization reaction between a bifunctional epoxy resin and a diester compound and / or a dihydroxy compound is carried out at a reaction temperature at which the used catalyst is not decomposed. If the reaction temperature is too high, the catalyst may be decomposed to stop the reaction, or the produced epoxy resin may be deteriorated. Conversely, if the temperature is too low, the reaction may not proceed sufficiently. For these reasons, the reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C. Moreover, reaction time is 1 to 12 hours normally, Preferably it is 3 to 10 hours. When using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave.

[Epoxy resin composition]
The epoxy resin composition of the present invention is an epoxy resin composition containing at least the above-described epoxy resin of the present invention and a curing agent. In addition, the epoxy resin composition of the present invention can be appropriately mixed with other additives such as an epoxy resin other than the epoxy resin of the present invention, an inorganic filler, a coupling agent, and an antioxidant as necessary. it can. The epoxy resin composition of the present invention is excellent in dielectric properties and heat resistance, has a low solution viscosity, and gives a cured product that sufficiently satisfies various physical properties required for various applications under good workability and productivity. is there.

[Curing agent]
A hardening | curing agent shows the substance which contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of an epoxy resin. In the present invention, even if what is usually called a “curing accelerator” is a substance that contributes to a crosslinking reaction and / or chain extension reaction between epoxy groups of an epoxy resin, it is regarded as a curing agent. To do.

The content of the curing agent in the epoxy resin composition of the present invention is preferably 0.1 to 100 weight in solid content with respect to 100 weight parts of the solid content of all epoxy resin components in the epoxy resin composition of the present invention. Part. Further, it is more preferably 80 parts by weight or less, and still more preferably 60 parts by weight or less.
In the present invention, the “solid content” means a component excluding the solvent, and includes not only a solid epoxy resin but also a semi-solid or viscous liquid material. In addition, the “all epoxy resin component” means that when the epoxy resin composition contains only the epoxy resin of the present invention, the epoxy resin of the present invention corresponds to the epoxy resin composition of the present invention and the epoxy resin described later. When it contains other epoxy resins, it corresponds to the total of the epoxy resin of the present invention and other epoxy resins described later.

  In the epoxy resin composition of the present invention, when other epoxy resin described later is included, the weight ratio of the solid content of the epoxy resin of the present invention and the other epoxy resin in the epoxy resin composition is 99 as described later. (That is, the content of the other epoxy resin is 1 to 99 parts by weight in a total of 100 parts by weight of the epoxy resin of the present invention and the other epoxy resin as a solid content). .

  There is no restriction | limiting in particular as a hardening | curing agent used for the epoxy resin composition of this invention, What is generally known as an epoxy resin hardening | curing agent can be used. Preferable ones from the viewpoint of improving heat resistance include phenolic curing agents, amide curing agents, imidazoles, and active ester curing agents. Examples of phenolic curing agents, amide curing agents, imidazole curing agents, active ester curing agents, cyanate ester curing agents, and other usable curing agents will be given below.

<Phenolic curing agent>
It is preferable to use a phenol-based curing agent as the curing agent from the viewpoint of improving the handleability of the resulting epoxy resin composition and the heat resistance after curing.

  Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3-bis. (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cle All novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2 , 4-Benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2, -Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, etc. The

  The phenolic curing agents mentioned above may be used alone or in a combination of two or more in any combination and ratio.

  When a phenolic curing agent is used as the curing agent, it is preferably used so that the equivalent ratio of functional groups in the phenolic curing agent to epoxy groups in all epoxy resin components is in the range of 0.8 to 1.5. Within this range, unreacted epoxy groups and functional groups of the curing agent are unlikely to remain, which is preferable.

<Amide-based curing agent>
It is preferable to use an amide type curing agent as the curing agent from the viewpoint of improving the heat resistance of the resulting epoxy resin composition.

  Examples of the amide-based curing agent include dicyandiamide and derivatives thereof, and polyamide resins.

  An amide type | system | group hardening | curing agent may be used only by 1 type, or may mix and use 2 or more types by arbitrary combinations and a ratio.

  The amide-based curing agent is preferably used in the range of 0.1 to 20% by weight with respect to the total of all the epoxy resin components and the amide-based curing agent as a solid content in the epoxy resin composition.

<Imidazole-based curing agent>
It is preferable to use imidazoles (imidazole-based curing agent) as the curing agent from the viewpoint of sufficiently proceeding the curing reaction and improving the heat resistance.

  Examples of imidazoles include 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s -Triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl s-Triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and epoxy resin and the above imidazoles And adducts are exemplified. In addition, since imidazoles have catalytic ability, they can generally be classified as curing accelerators described later, but in the present invention, they are classified as curing agents.

  The imidazoles listed above may be used alone or in combination of two or more in any combination and ratio.

  It is preferable to use imidazoles in the range of 0.1 to 20% by weight with respect to the total of all epoxy resin components and imidazoles as a solid content in the epoxy resin composition.

<Active ester curing agent>
It is preferable to use an active ester curing agent as the curing agent from the viewpoint of improving the heat resistance and dielectric properties of the resulting cured product.

  Examples of the active ester curing agent include compounds having two or more ester groups having high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds. Among them, phenol esters obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group are more preferable. Specific examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. As aromatic compounds having a phenolic hydroxyl group, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, Examples include dicyclopentadienyl diphenol and phenol novolac.

  As the active ester curing agent, a compound having an internal ester type structure is preferably used from the viewpoint of improving heat resistance, and specifically, a compound such as polyarylate resin can be used as the curing agent.

  The active ester curing agents listed above may be used alone or in a combination of two or more in any combination and ratio.

  The active ester curing agent is used so that the equivalent ratio of the active ester group in the active ester curing agent to the epoxy group in all epoxy resin components in the epoxy resin composition is in the range of 0.2 to 2.0. It is preferable.

<Cyanate ester curing agent>
It is preferable to use a cyanate ester compound as a curing agent from the viewpoint of improving the heat resistance and dielectric properties of the resulting cured product.

  Examples of the cyanate ester compound include 2,2-bis (4-cyanatephenyl) propane (bisphenol A type cyanate resin), bis (3,5-dimethyl-4-cyanatephenyl) methane, and 2,2-bis (4 -Cyanate phenyl) ethane, etc., or aromatic cyanate ester compounds such as derivatives thereof. These may be used alone or in combination of two or more.

<Other curing agents>
Examples of the curing agent other than the above-mentioned phenol-based curing agent, amide-based curing agent, imidazoles, and active ester-based curing agent that can be used in the epoxy resin composition of the present invention include an amine-based curing agent (however, the third Except for secondary amines), acid anhydride curing agents, tertiary amines, organic phosphines, phosphonium salts, tetraphenyl boron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing Agents, blocked isocyanate curing agents, and the like. The other hardening | curing agent quoted above may be used only by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio.

[Other epoxy resins]
The epoxy resin composition of the present invention can contain other epoxy resins different from the epoxy resin of the present invention in addition to the epoxy resin of the present invention. By using other epoxy resins, the insufficient physical properties can be compensated or various physical properties can be improved.

  The other epoxy resin preferably has two or more epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin. Bisphenol Z type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, etc. Various epoxy resins can be used. These can be used alone or as a mixture of two or more.

  In the epoxy resin composition of the present invention, when the epoxy resin of the present invention and another epoxy resin are used, the total epoxy resin component as a solid content, that is, a total of 100 weights of the epoxy resin of the present invention and the other epoxy resin The amount of the other epoxy resin in the part is preferably 1 part by weight or more, more preferably 5 parts by weight or more, still more preferably 10 parts by weight or more, while preferably 99 parts by weight or less. More preferably 95 parts by weight or less, still more preferably 90 parts by weight or less. When the ratio of the other epoxy resin is equal to or more than the above lower limit value, the effect of improving physical properties by blending the other epoxy resin can be sufficiently obtained. On the other hand, when the ratio of the other epoxy resin is not more than the above upper limit value, the effect of the epoxy resin of the present invention is sufficiently exhibited, which is preferable from the viewpoint of obtaining heat resistance and low solution viscosity.

[solvent]
The epoxy resin composition containing the epoxy resin of the present invention may be diluted by blending a solvent in order to appropriately adjust the viscosity of the epoxy resin composition at the time of handling during coating film formation. In the epoxy resin composition of the present invention, the solvent is used in order to ensure the handleability and workability in the molding of the epoxy resin composition, and the amount used is not particularly limited. In the present invention, the term “solvent” and the above-mentioned term “solvent” are distinguished from each other depending on the form of use, but the same or different ones may be used independently.

  Examples of the solvent that can be contained in the epoxy resin composition containing the epoxy resin of the present invention include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, and ethers such as ethylene glycol monomethyl ether. Amides such as N, N-dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene. The solvent mentioned above may be used only by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio.

[Other ingredients]
In the epoxy resin composition containing the epoxy resin of the present invention, components other than those listed above (sometimes referred to as “other components” in the present invention) for the purpose of further improving the functionality. May be included. Examples of such other components include thermosetting resins other than epoxy resins, photocurable resins, curing accelerators (except for those included in “curing agents”), UV inhibitors, antioxidants, Examples include coupling agents, plasticizers, fluxes, flame retardants, colorants, dispersants, emulsifiers, low elasticity agents, diluents, antifoaming agents, ion trapping agents, inorganic fillers, and organic fillers.

[Cured product]
A cured product obtained by curing the epoxy resin of the present invention with a curing agent has an excellent balance of dielectric properties, heat resistance, etc., and exhibits good cured properties. The term “curing” as used herein means that the epoxy resin composition is intentionally cured by heat and / or light or the like, and the degree of curing may be controlled by desired physical properties and applications. The degree of progress of the curing reaction may be completely cured or semi-cured, and is not particularly limited. However, the reaction rate of the curing reaction between the epoxy group and the curing agent is usually 5 to 95%.

  The curing method of the epoxy resin composition when curing the epoxy resin composition of the present invention to obtain a cured product varies depending on the blending component and blending amount in the epoxy resin composition, but is usually 60 to 80 to 280 ° C. Heating conditions of ~ 360 minutes are mentioned. This heating is preferably performed in a two-stage process of primary heating at 80 to 160 ° C. for 10 to 90 minutes and secondary heating at 120 to 200 ° C. for 60 to 150 minutes, and the glass transition temperature (Tg) is In the blending system exceeding the temperature of the secondary heating, it is preferable to further perform the tertiary heating at 150 to 280 ° C. for 60 to 120 minutes. Performing secondary heating and tertiary heating in this manner is preferable from the viewpoint of reducing poor curing and residual solvent.

  When producing a resin semi-cured product, it is preferable to advance the curing reaction of the epoxy resin composition to such an extent that the shape can be maintained by heating or the like. When the epoxy resin composition contains a solvent, most of the solvent is usually removed by heating, decompression, air drying, etc., but 5 wt% or less of the solvent is left in the resin semi-cured product. Also good.

[Use]
The epoxy resin of the present invention can provide an epoxy resin having a low solution viscosity while maintaining the excellent heat resistance and dielectric properties of the polyphenylene ether skeleton, and the epoxy resin composition containing the epoxy resin has dielectric properties, There is an effect that a cured product having excellent heat resistance is provided with good handleability, workability, and productivity. For this reason, it can be applied to various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical / electronic parts, etc., especially as insulating castings, laminated materials, sealing materials, etc. in the electrical / electronic field. Useful. Examples of the use of the epoxy resin of the present invention and the epoxy resin composition containing the epoxy resin include multilayer printed wiring boards, laminates for electric and electronic circuits such as capacitors, film adhesives, adhesives such as liquid adhesives, and semiconductors. A sealing material, an underfill material, a 3D-LSI interchip fill, an insulating sheet, a prepreg, a heat dissipation substrate, and the like are exemplified, but the invention is not limited thereto.

[Laminated board for electrical and electronic circuits]
As described above, the epoxy resin composition of the present invention can be suitably used for applications of laminates for electric / electronic circuits. In the present invention, the “laminate for electric / electronic circuit” is a laminate of a layer containing the epoxy resin composition of the present invention and a conductive metal layer, and is electrically conductive with the layer containing the epoxy resin composition of the present invention. As long as the conductive metal layer is laminated, it can be used as a concept including, for example, a capacitor, not an electric / electronic circuit. In addition, the layer which consists of 2 or more types of epoxy resin compositions may be formed in the laminated board for electric / electronic circuits, and the epoxy resin composition of this invention should just be used in at least 1 layer. . Two or more kinds of conductive metal layers may be formed.

  The thickness of the layer made of the epoxy resin composition in the laminate for electric / electronic circuit is usually about 10 to 200 μm. The thickness of the conductive metal layer is usually about 0.2 to 70 μm.

<Conductive metal>
Examples of the conductive metal in the laminate for electric / electronic circuit include metals such as copper and aluminum, and alloys containing these metals. In the present invention, for the conductive metal layer of the laminate for electric / electronic circuit, a metal foil of these metals or a metal layer formed by plating or sputtering can be used.

<Manufacturing method of laminate for electric / electronic circuit>
As a manufacturing method of the laminated board for electric / electronic circuits in this invention, the following methods are mentioned, for example.
(1) A non-woven fabric or cloth using inorganic and / or organic fiber materials such as glass fiber, polyester fiber, aramid fiber, cellulose, and nanofiber cellulose is impregnated with the epoxy resin composition of the present invention to form a prepreg; After providing a conductive metal layer by conductive metal foil and / or plating, a circuit is formed using a photoresist or the like, and a necessary number of such layers are stacked to form a laminate.
(2) The prepreg of (1) above is used as a core material, and a layer made of the epoxy resin composition of the present invention and a conductive metal layer are laminated thereon (build-up method). The layer made of the epoxy resin composition may contain an organic and / or inorganic filler.
(3) Without using the core material, only the layer made of the epoxy resin composition of the present invention and the conductive metal layer are alternately laminated to obtain a laminate for an electric / electronic circuit.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited at all by the following example. In addition, the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value. A range defined by a combination of values of the following examples or values of the examples may be used.

[Method for evaluating physical properties and characteristics]
In the following examples and comparative examples, physical properties and characteristics were evaluated by the methods described in 1) to 5) below.

1) Weight average molecular weight (Mw) and number average molecular weight (Mn)
Using "HLC-8320GPC apparatus" manufactured by Tosoh Corporation, under the following measurement conditions, as standard polystyrene, TSK Standard Polystyrene: F-128 (Mw: 1,090,000, Mn: 1,030,000), F-10 (Mw: 106,000, Mn: 103,000), F-4 (Mw: 43,000, Mn: 42,700), F-2 (Mw: 17,200, Mn: 16,900) A-5000 (Mw: 6,400, Mn: 6,100), A-2500 (Mw: 2,800, Mn: 2,700), A-300 (Mw: 453, Mn: 387) were used. A calibration curve was prepared, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured as polystyrene conversion values.
Column: “TSKGEL SuperHM-H + H5000 + H4000 + H3000 + H2000” manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Flow rate: 0.5 ml / min
Detection: UV (wavelength 254 nm)
Temperature: 40 ° C
Sample concentration: 0.1% by weight
Injection volume: 10 μl

2) Number of m The value of m in the formula (1) was calculated from the number average molecular weight determined above.

3) Epoxy equivalent Measured according to JIS K 7236 and expressed as a solid content converted value.

4) Solution viscosity A solution of 50% by weight of epoxy resin dissolved in an equivalent amount of cyclohexanone / methyl ethyl ketone mixed in a fixed amount is placed in a Cannon-Fenske viscometer and sampled in a 25 ° C constant temperature water bath. The flow time was measured. The viscosity of the epoxy resin solution was calculated from the measurement time and the coefficient of the viscometer.

5) Heat resistance of cured product: Glass transition temperature (Tg)
The epoxy resin composition solution was applied to a separator (silicone-treated polyethylene terephthalate film, thickness: 100 μm) with an applicator, dried and cured at 160 ° C. for 1.5 hours, and then at 200 ° C. for 1.5 hours, and the thickness was about A cured epoxy resin film of 50 μm was obtained. Using “DSC7020” manufactured by SII Nanotechnology, the glass transition temperature was measured by raising the temperature from 30 to 250 ° C. at 10 ° C./min. The glass transition temperature here was measured based on “midpoint glass transition temperature: Tmg” described in JIS K7121 “Plastic Transition Temperature Measurement Method”.

[Raw materials]
The raw materials, catalysts, solvents and solvents used in the following examples and comparative examples are as follows.

[Bifunctional epoxy resin]
(A-1): Mitsubishi Chemical Corporation product name “jER YX4000” (3,3 ′, 5,5′-tetramethyl-4,4′-biphenoldiglycidyl ether, epoxy equivalent 186 g / equivalent)
(A-2): Mitsubishi Chemical Corporation product name “jER 828US” (bisphenol A type epoxy resin, epoxy equivalent: 185 g / equivalent)

[Bisphenol compounds or diester compounds]
(B-1): 4,4 ′-(3,3,5-trimethylcyclohexylidene) bisphenol (expressed by the above formula (17), and having a chemical structure represented by the formula (2) ′ as A ′ Corresponds to bisphenol compounds. (Honshu Chemical Co., Ltd. product name: BisP-HTG, hydroxyl group equivalent: 155 g / equivalent)
(B-2): Biphenol (corresponding to a compound having a chemical structure represented by the formula (17) and represented by the formula (2) ′ as A ′) (hydroxyl equivalent: 93)
(B-3): 4,4 ′-(fluorene-9,9-diyl) bis (2-methylphenol) (a chemistry represented by the formula (17) and represented by the formula (2) ′ as A ′ It corresponds to a bisphenol compound having a structure.) (Honshu Chemical Co., Ltd. product name: BisOC-FL, hydroxyl group equivalent: 189 g / equivalent)
(B-4): 4,4′-diacetoxybiphenyl (corresponding to a compound having a chemical structure represented by the formula (17) and represented by the formula (2) ′ as A ′) (active equivalent: 135)

  The structural formulas of (B-1) to (B-4) are as follows.

[Terminal OH / polyphenylene ether compound]
(P-1): Product name “NORYL SA-90” (terminal OH / polyphenylene ether compound) (hydroxyl group equivalent: about 848, number average molecular weight: about 1700) manufactured by SABIC

  The structural formula of (P-1) is as follows.

(The average value of r and r 'is approximately 6.3)

[catalyst]
(C-1): Tetramethylammonium hydroxide (27 wt% aqueous solution)
(C-2): 4- (dimethylamino) pyridine

[Solvent / Solvent]
(S-1): Cyclohexanone (S-2): Methyl ethyl ketone (MEK)

[Other epoxy resins]
(E-1): “YX6954BH30”: a high molecular weight epoxy resin (3,3 ′, 5,5′-tetramethyl-4,4′-biphenoldiglycidyl ether and 4,4 ′-( 1-phenylethylidene) diphenol copolymer, weight average molecular weight: 35,000, resin content 30% by weight, cyclohexanone 35% by weight, methyl ethyl ketone 35% by weight)

[Curing agent]
(D-1): “PSM6200”: phenol novolak (hydroxyl equivalent: 103) manufactured by Gunei Chemical Industry Co., Ltd., used as a 50 wt% cyclohexanone solution (D-2): 2-ethyl-4 (5)- Methylimidazole (product name: jER Cure (registered trademark) EMI24 manufactured by Mitsubishi Chemical Corporation), used as a 20% by weight methyl ethyl ketone solution

[Leveling agent]
S-651: Fluorine-based surfactant (nonionic type) manufactured by AGC Seimi Chemical Co., Ltd.

[Production and evaluation of epoxy resins: heat resistance]
<Examples 1-1 to 1-9, Comparative Examples 1-1 to 1-4>
A bifunctional epoxy resin, a terminal OH / polyphenylene ether compound, a bisphenol compound or a diester compound, a catalyst, and a reaction solvent were put in a reaction vessel equipped with a stirrer according to the formulation shown in Table 1, and in a nitrogen gas atmosphere, Table 1 The reaction was carried out at the reaction time and reaction temperature described in. Then, the solvent for dilution was added and it adjusted so that solid content concentration might be 50 weight%. The result of having analyzed about obtained resin is shown in Table-2.

[Production and evaluation of epoxy resin composition / cured product: heat resistance]
<Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-4>
Mix the epoxy resins obtained in Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-4 with other epoxy resins and curing agents in the proportions shown in Table 3, and stir well. An epoxy resin composition was obtained. About this epoxy resin composition, the glass transition temperature was measured by the above-mentioned method. The results are shown in Table-3.

From the results of Tables 2 and 3, the following can be understood.
That is, Comparative Example 1-1 that does not use a bisphenol compound as a raw material has only one type of structure (A-1) derived from the raw material epoxy resin in Formula (1). Compared with, the solution viscosity is high and the handleability is inferior. On the other hand, as for the heat resistance of the composition and the cured product, the decrease in Tg of Example 2-1 is within 10 ° C. as compared with Comparative Example 2-1, and even when a bisphenol compound is used, it depends on the polyphenylene ether skeleton. It can be seen that high heat resistance can be maintained. Example 1-2 and Comparative Example 1-2, Examples 1-3, 1-4, 1-6, 1-7 and Comparative Example 1-3, Example 1-5 and Comparative Example 1-4, and The same can be seen from the comparison of the blends and cured products. Therefore, it is clear that the epoxy resin of the present invention has a low solution viscosity and excellent handleability while maintaining the excellent heat resistance of the polyphenylene ether skeleton.

  The epoxy resin of the present invention can provide an epoxy resin having a low solution viscosity while maintaining the excellent heat resistance and dielectric properties of the polyphenylene ether skeleton, and the epoxy resin composition containing the epoxy resin has dielectric properties, There is an effect that a cured product having excellent heat resistance is provided with good handleability, workability, and productivity. For this reason, it can be applied to various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical / electronic parts, etc., especially as insulating castings, laminated materials, sealing materials, etc. in the electrical / electronic field. Useful. Examples of the use of the epoxy resin of the present invention and the epoxy resin composition containing the epoxy resin include multilayer printed wiring boards, laminates for electric and electronic circuits such as capacitors, film adhesives, adhesives such as liquid adhesives, and semiconductors. A sealing material, an underfill material, a 3D-LSI interchip fill, an insulating sheet, a prepreg, a heat dissipation substrate, and the like are exemplified, but the invention is not limited thereto.

Claims (17)

An epoxy resin represented by the following formula (1).

(In the formula (1), A represents a structure selected from the group represented by the structure represented by the formula (2) and a divalent hydrocarbon group having 1 to 13 carbon atoms (hereinafter referred to as “structure (A-1)”). Two or more of the above and a structure represented by the formula (3),
R ¹ and R ² are both a group represented by the formula (5), or one is a group represented by the formula (5) and the other is a hydrogen atom,
R ³ is a hydrogen atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group,
m is an average value of the number of repetitions and represents a number of 0 to 500.
In formula (2), X represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —CO—. A group selected from
R ^{4 to} R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, And a group selected from alkynyl groups having 1 to 12 carbon atoms.
In formula (3), Y includes the structure represented by formula (4),
R ^{12 to} R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, And a group selected from an alkynyl group having 1 to 12 carbon atoms,
p and q are average values of the number of repetitions, and each independently represents a number of 0 to 30.
In formula (4), Z represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and —CO—. A group selected from
R ^{29 to} R ³⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, And a group selected from alkynyl groups having 1 to 12 carbon atoms. )   The epoxy resin of Claim 1 in which A in Formula (1) contains 60-90 mol% of structures (A-1). The epoxy resin according to claim 1 or 2, wherein the structure (A-1) includes one or more of structures represented by the following formulas (6) to (15).

The epoxy resin according to any one of claims 1 to 3, wherein the structure represented by the formula (3) includes a structure represented by the following formula (16).

(In Formula (16), Y, p, and q are synonymous with Y, p, and q in Formula (3), respectively.) An epoxy resin that is a reaction product of a bifunctional epoxy resin represented by the following formula (17), a compound represented by the following formula (18), and a compound represented by the following formula (19).

(In Formula (17) and Formula (18), A ′ is a structure selected from the group represented by Formula (2) ′ and a divalent hydrocarbon group having 1 to 13 carbon atoms (hereinafter, “ Including two or more of structure (A′-1) ”,
n is an average value of the number of repetitions and represents an integer of 0 to 6.
In Formula (18), R ′ ³ is a hydrogen atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group.
In formula (2) ′, X ′ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and — A group selected from CO-
R ′ ^{4 to} R ′ ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 1 to 12 carbon atoms. A group selected from a group and an alkynyl group having 1 to 12 carbon atoms.
In Formula (19), Y ′ includes a structure represented by Formula (4) ′,
R ′ ^{12 to} R ′ ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 1 to 12 carbon atoms. A group selected from a group and an alkynyl group having 1 to 12 carbon atoms,
R ′ ²⁸ is a hydrogen atom, an aliphatic carbonyl group having 1 to 10 carbon atoms, or an aromatic carbonyl group,
p ′ and q ′ are average values of the number of repetitions, and each independently represents a number of 0 to 30.
In formula (4) ′, Z ′ represents a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ —, and — A group selected from CO-
R ′ ^{29 to} R ′ ³⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl having 1 to 12 carbon atoms. A group selected from a group and an alkynyl group having 1 to 12 carbon atoms. )   The amount of the compound represented by formula (18) is the total number of moles of the bifunctional epoxy resin represented by formula (17), the compound represented by formula (18) and the compound represented by formula (19). The epoxy resin of Claim 5 which is 3-20 mol% with respect to. The epoxy resin according to claim 5 or 6, wherein the structure (A'-1) includes one or more of structures represented by the following formula (6) 'to formula (15)'.

The epoxy resin according to any one of claims 5 to 7, wherein the compound represented by the formula (19) includes a compound represented by the following formula (20).

(In Formula (20), Y ', p', and q 'are synonymous with Y', p ', and q' in Formula (19).)   The epoxy resin according to any one of claims 1 to 8, wherein the weight average molecular weight is 2,000 to 50,000.   The epoxy resin according to any one of claims 1 to 9, wherein an epoxy equivalent is 400 g / equivalent or more and 15,000 g / equivalent or less.   The epoxy resin composition containing the epoxy resin of this invention of any one of Claim 1 to 10, and a hardening | curing agent.   The epoxy resin composition of Claim 11 which contains 0.1-100 weight part of hardening | curing agents with respect to 100 weight part of epoxy resins of this invention.   Furthermore, other epoxy resins other than the epoxy resin of the present invention are included, and 1 to 99 parts by weight of the other epoxy resins are included in a total of 100 parts by weight of the epoxy resin of the present invention and other epoxy resins as a solid content. The epoxy resin composition according to 11 or 12.   The epoxy resin composition of Claim 13 which contains 0.1-100 weight part of hardening | curing agents with respect to a total of 100 weight part of the epoxy resin of this invention, and another epoxy resin.   The hardener is at least one selected from the group consisting of phenolic hardeners, amide hardeners, imidazoles, active ester hardeners, and cyanate ester hardeners. The epoxy resin composition as described.   The laminated board for electrical / electronic circuits which uses the epoxy resin composition of any one of Claim 11 to 15.   Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claim 11 to 15.