JP2016089165A - Epoxy resin, epoxy resin composition, cured product, laminate for electric/electronic circuit, and method for producing epoxy resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin having excellent film forming properties, and a cured product having excellent chemical resistance.SOLUTION: An epoxy resin is represented by formula (1), having components of formulas (2) and (3), with Mw amount of 5000-200000 and epoxy equivalent of 2000-50000 g/equivalent.SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin having excellent film forming properties. The present invention also relates to an epoxy resin composition containing the epoxy resin and a curing agent, a cured product excellent in chemical resistance (particularly solvent resistance), 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 insulation casting, laminated materials, sealing materials and the like. In recent years, multilayer circuit boards used in electrical and electronic equipment have been reduced in size, weight and functionality, and further multilayered, denser, thinner, lighter and more reliable and molded. Improvements in workability are required.

One of the important performances required for epoxy resins used as materials for electrical / electronic components such as laminates for electrical / electronic circuits is chemical resistance (particularly solvent resistance). If the chemical resistance (especially solvent resistance) is low, it may cause a problem in a process such as cleaning. It may also lead to long-term reliability degradation of the product.
In the build-up method used for highly integrated multi-layer substrates, higher multi-layers and thinner insulating layers are progressing, and not only chemical resistance (especially solvent resistance) but also film-forming properties and dielectric properties Balance with various properties such as heat resistance is required. In particular, since it is necessary to form an insulating material into a film, the film forming property is an essential characteristic.

Recently, an example has been disclosed in which polarization is suppressed by esterifying a secondary hydroxyl group generated by a reaction between an epoxy group and a curing agent to improve hygroscopicity and dielectric properties.
Patent Document 1 discloses a method for producing an epoxy resin in which a secondary hydroxyl group is esterified by reacting an acylated polyphenol compound with an epoxy resin.
The esterified epoxy resin disclosed here has an epoxy equivalent of 904 g / equivalent at the maximum, and since the molecular weight is not large, film forming property cannot be expected. In recent years, the build-up material is mainly in the form of a film, and a high molecular weight type epoxy resin having a film-forming property is demanded. However, in Patent Document 1, high molecular weight is not considered, and the high molecular weight is considered. There is no description about the manufacturing conditions for realizing the process. Further, in the examples, tetrabutylammonium bromide is used as a catalyst, and according to the study by the present inventors, it has been found that it is difficult to achieve a high molecular weight until the film-forming property is exhibited with this catalyst. ing. Furthermore, the active use of halogen compounds is never preferred due to the recent increase in awareness of environmental problems.

Further, in Patent Document 2, a low hygroscopic property is obtained by using a thermoplastic resin obtained by esterifying a secondary hydroxyl group of a phenoxy resin (high molecular weight epoxy resin) in a subsequent step and blending a thermosetting resin therein. A thermosetting resin composition that can improve adhesion to a conductor layer while maintaining dielectric properties is disclosed.
Although it is possible to obtain a high molecular weight type esterified resin by esterifying the phenoxy resin in a subsequent step, according to the study by the present inventors, in this method, hydrogen chloride and carboxylic acid produced during the reaction are used. It is known that the terminal epoxy group disappears due to the influence of acid. As described in the literature, this high molecular weight esterified resin is a thermoplastic resin and cannot participate in the curing reaction. Since it is not fixed in the cross-linked structure, the heat resistance, dielectric properties, chemical resistance (solvent resistance), etc. expected when involved in the curing reaction may not be sufficiently exhibited.

JP-A-8-333427 WO2005 / 095517

The subject of this invention is providing the epoxy resin excellent in film forming property. Moreover, the epoxy resin composition containing this is providing the hardened | cured material excellent in chemical resistance (especially solvent resistance).
As a result of intensive studies, the present inventors have succeeded in producing a polymer-type esterified epoxy resin having an epoxy group at the molecular end, and found that the esterified epoxy resin is excellent in film forming properties. Moreover, it discovered that the hardened | cured material which consists of a composition using the high molecular weight esterified epoxy resin of this invention was excellent in chemical resistance (especially solvent resistance). That is, the gist of the present invention resides in the following [1] to [11].
[1] It is represented by the following formula (1), has a weight average molecular weight of 5,000 to 200,000, an epoxy equivalent of 2,000 to 50,000 g / equivalent, and an epoxy equivalent of a number average molecular weight or less. Epoxy resin.

(In the above formula (1), A includes the chemical structure represented by the above formula (2), R ¹ and R ² may be different from each other, and may be a hydrogen atom or a chemistry represented by the above formula (3). And at least one of them is a group represented by the above formula (3), 5 mol% or more of R ³ is an aliphatic carbonyl group or aromatic carbonyl group having 1 to 10 carbon atoms, and the remainder is hydrogen. N is an average value of the number of repetitions and is from 5 to 500. In the above formula (2), X ¹ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ — and —CO—, each of R ^{4 to} R ¹¹ is independently a hydrogen atom or 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 alkeni having 1 to 12 carbon atoms And a group arbitrarily selected from a C 1-12 alkynyl group.)
[2] The epoxy resin according to [1], wherein the chemical structure represented by the formula (2) is the following formula (4) and / or the following formula (5).

[3] An epoxy resin composition comprising the epoxy resin according to [1] or [2] and a curing agent.
[4] 0.1 to 1 solid content of the curing agent relative to 100 weight parts of the solid content of the epoxy resin.
The epoxy resin composition according to [3], including 00 parts by weight.
[5] The method according to [3] or [4], including the epoxy resin and another epoxy resin, wherein a weight ratio of the solid content between the epoxy resin and the other epoxy resin is 99/1 to 1/99. Epoxy resin composition.
[6] The epoxy resin composition according to [5], including 0.1 to 100 parts by weight of the curing agent in solid content with respect to a total of 100 parts by weight of solid content of the epoxy resin and another epoxy resin.
[7] In any one of [3] to [6], the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amide curing agent, an imidazole, and an active ester curing agent. The epoxy resin composition as described.
[8] A laminate for an electric / electronic circuit using the epoxy resin composition according to any one of [3] to [7].
[9] A cured product obtained by curing the epoxy resin composition according to any one of [3] to [7].
[10] A bifunctional epoxy resin represented by the following formula (6) is reacted with a diester compound represented by the following formula (7), the weight average molecular weight is 5,000 to 200,000, and the epoxy equivalent is The manufacturing method of the epoxy resin which obtains the epoxy resin of following formula (1) 'whose 2,000-50,000g / equivalent and epoxy equivalent are number average molecular weights or less.

(In the above formula (1) ′, A ′ includes the chemical structure represented by the above formula (2) ′, and R ′ ¹ and R ′
² may be different from each other, and is a hydrogen atom or a chemical structure represented by the above formula (3) ′, and at least one of them is a group represented by the above formula (3) ′. 5 ′ mol% or more of R ′ ³ is an aliphatic carbonyl group or aromatic carbonyl group having 1 to 10 carbon atoms, the remainder is a hydrogen atom, and n is an average value of the number of repetitions and is 5 or more and 500 or less. In the above formula (2) ′, X ′ ¹ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ — and 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, or a group having 6 to 12 carbon atoms. It is a group arbitrarily selected from an aryl group, an alkenyl group having 1 to 12 carbon atoms, and an alkynyl group having 1 to 12 carbon atoms. )

(In the formula (6) and / or (7), A 'is the above formula (2)' includes a chemical structure represented by, R ^'3 5 mole% or more aliphatic carbonyl having 1 to 10 carbon atoms A group or an aromatic carbonyl group, the remainder is a hydrogen atom, m is an average value of the number of repetitions, and is 0 or more and 6 or less.)
[11] The method for producing an epoxy resin according to [10], wherein the chemical structure represented by the formula (2) ′ is the following formula (8) and / or the following formula (9).

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin excellent in film forming property can be provided. Moreover, the epoxy resin composition using this epoxy resin can provide a cured product excellent in chemical resistance (particularly solvent resistance). 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.

〔Epoxy resin〕
The epoxy resin of the present invention is represented by the following formula (1), has a weight average molecular weight of 5,000 to 200,000, an epoxy equivalent of 2,000 to 50,000, and an epoxy equivalent of a number average molecular weight or less. It is.

(In the above formula (1), A includes the chemical structure represented by the above formula (2), R ¹ and R ² may be different from each other, and may be a hydrogen atom or a chemistry represented by the above formula (3). And at least one of them is a group represented by the above formula (3), R ³ is a substituent containing an aliphatic or aromatic group having 1 to 10 carbon atoms, and n is an average value of the number of repetitions. And in the formula (2), X ¹ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C. (CF ₃ ) ₂ — and —CO— are groups selected, and 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, carbon Arbitrary group having 6 to 12 carbon atoms, alkenyl group having 1 to 12 carbon atoms, and alkynyl group having 1 to 12 carbon atoms are arbitrarily selected The group to be selected.)
The epoxy resin of this invention has the characteristics that it is excellent in film forming property. In the above formula (1), it has a molecular weight sufficient to express the film-forming property and has an epoxy group at the molecular end, so that it is incorporated into the crosslinked structure at the time of the curing reaction, whereby the chemical resistance of the cured product ( In particular, it is estimated that the solvent resistance is improved.

<Chemical structure>
In the formula (1), A includes a chemical structure represented by the formula (2). In the formula (2), X ¹ is 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-.
Here, examples of the divalent hydrocarbon group having a carbon number of 1 to 13 in the X ¹ in the formula (2) include the following. For example, —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —CHPh—, —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 and the like.

Among these, X ¹ is a direct bond, —CH ₂ —, —CH (CH ₃ ) because the lower the degree of rotational freedom of the two aromatic rings tends to be superior in chemical resistance (particularly solvent resistance). _{-, - C (CH 3)} 2 -, - C (CF 3) 2 -, - CHPh -, - C (CH 3) Ph -, - CPh 2 -, 9,9- fluorenylene group, 1,1-cyclohexylene Two fragrances 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 —, 9,9-fluorenylene group, 3,3,5-trimethyl-1,1-cyclohexylene Group, 1,1-cyclododecylene group is more preferable, direct bond, —C (CF ₃ ) ₂ —, 9,9-fluorenylene group, 3,3,5-trimethyl-1,1-cyclohexylene group, 1,1 -A cyclododecylene group is further preferred, and a direct bond is particularly preferred.

When X ¹ is a direct bond, the biphenyl skeleton is 2,2′-biphenyl skeleton, 2,3′-biphenyl skeleton, 2,4′-biphenyl skeleton, 3,3′-biphenyl skeleton, 3, Either a 4′-biphenyl skeleton or a 4,4′-biphenyl skeleton may be used, but a 4,4′-biphenyl skeleton is preferred. On the other hand, X ¹ is —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —CHPh—, —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— and the like, the bonding positions in these aromatic rings are 2,2′-position, 2,3′-position, 2,4′-position, 3,3′-position, Either the 3,4′-position or the 4,4′-position may be used, but the 4,4′-position is preferred.

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 following are mentioned as a C1-C12 alkyl group of R < ⁴ > -R < ¹¹ > in the said Formula (2). 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. .

Also, there are the following as an alkoxy group having from 1 to 12 carbon atoms ^R 4 ^{to R 11} in the formula (2). 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, And vinyl naphthyl group.
Examples of the alkenyl group having 2 to 12 carbon atoms of R ^{4 to} R ¹¹ in the formula (2) include the following. 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.

Examples of the alkynyl group having 2 to 12 carbon atoms represented by R ^{4 to} R ¹¹ in the formula (2) include the following. 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 flexibility and heat resistance during film formation may be reduced. ^Also, when R 4 ^{to R 11} is a hydrocarbon group having 1 to 12 carbon atoms an alkyl group having 1 to 4 carbon ^atoms, preferably the substitution number of R 4 ^{to R 11} is 2 or 4, In addition, R ^{When the} number of substitutions of ^{4 to} R ¹¹ is 2, the alkyl group is preferably in the 2-position and 2′-position, and when the number of substitutions of R ^{4 to} R ¹¹ is 4, the alkyl group is 2 It is preferably in the -position, 2'-position, 6-position and 6'-position.

In the formula (1), R ¹ and R ² may be different from each other, and are a hydrogen atom or a chemical structure represented by the formula (3), at least one of which is represented by the formula (3). It is a group.
5 mol% or more of R ³ in the formula (1) is an aliphatic carbonyl group or aromatic carbonyl group having 1 to 10 carbon atoms, and the remainder is a hydrogen atom.

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.

Examples of the aromatic carbonyl group having 1 to 10 carbon atoms (substantially 5 to 10 carbon atoms) of R ³ in the formula (1) include a benzoyl group, a methylbenzoyl group, a methoxybenzoyl group, and a furylcarbonyl group. Of these, a benzoyl group is preferred.
The epoxy resin of the present invention is usually a mixture of molecules having these ends or molecules having different repeating numbers n described below.

  In said Formula (1), n is a repeating number and is an average value. The range of the value is 5 or more from the viewpoint of film forming property, and is 500 or less from the viewpoint of the handleability of the resin. From the viewpoint of further improving the film forming property, it is preferably 10 or more, more preferably 15 or more, while from the viewpoint of further improving the handleability of the resin, it is preferably 200 or less. Preferably it is 100 or less. The n 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.

<Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the epoxy resin of this invention is 5,000-200,000. When the weight average molecular weight is lower than 5,000, the film-forming property is lowered, and when it is higher than 200,000, the handling of the resin becomes difficult. The weight average molecular weight (Mw) of the epoxy resin of the present invention is preferably 10,000 or more, more preferably 15,000 or more from the viewpoint of improving the film forming property, and from the viewpoint of improving the handleability. 160,000 or less, more preferably 120,000 or less, and still more preferably 80,000 or less. 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 this invention is the range of 2,000-50,000 g / equivalent, and 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 (4) with a diester compound represented by the following formula (5). Theoretically, it can be synthesized by a method of acylating the secondary hydroxyl group of phenoxy resin (high molecular weight epoxy resin) synthesized by a known method in the subsequent step, but it is actually generated during the acylation reaction. This method is preferably used because the terminal epoxy group disappears due to hydrogen chloride or carboxylic acid.

(In the formula (4) and / or (5), A 'is the above formula (2)' includes a chemical structure represented by, R ^'3 5 mole% or more aliphatic carbonyl having 1 to 10 carbon atoms A group or an aromatic carbonyl group, and the remainder is a hydrogen atom, m is an average value of the number of repetitions and is 0 or more and 6 or less, In the above formula (2) ′, X ′ ¹ is a direct bond, 1 to 1 carbon atoms. 13 divalent hydrocarbon groups, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ — and —CO—, wherein 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, or an alkynyl group having 1 to 12 carbon atoms It is a group arbitrarily selected from groups.)
The bifunctional epoxy resin used for the production of the epoxy resin of the present invention is an epoxy resin represented by the above formula (4). For example, a bisphenol compound represented by the following formula (6) is obtained by a known method. Examples include epoxy resins obtained by condensation with epihalohydrin.

(The definition of A ′ in the above formula (6) is the same as that in the above formula (4) and / or (5).)
Moreover, the diester compound used for manufacture of the epoxy resin of this invention is represented by the said Formula (5), for example, the bisphenol type compound represented by the said Formula (6) is acid chloride and an acid anhydride. Alternatively, it is obtained by acylation by a condensation reaction with carboxylic acid or the like.
In the formula (4) and / or (5), A ′ may or may not contain the chemical structure represented by the formula (2) ′, but A ′ in the formula (4) may be included. When “does not include the formula (2)”, the formula (5) necessarily includes the chemical structure represented by the formula (2) ′. on the other hand,
In the formula (6), A ′ may or may not contain the chemical structure represented by the formula (2) ′, but A ′ in the formula (5) may be represented by the formula (2). When 'is not included, the formula (6) necessarily includes the chemical structure represented by the formula (2)'. That is, the epoxy resin of the present invention necessarily includes the chemical structure represented by the formula (2) ′, and as long as this is satisfied, the chemical structure of the formula (2) ′ is a bifunctional epoxy resin. And a diester compound, and the ratio of the chemical structure is not limited.

However, considering the reactivity with the epoxy group, it is preferable that the formula (5) necessarily includes the structure represented by the formula (2) ′.
Formula (2) 'in R' ⁴ to R ^'11 defined preferred ones are the same as the ^R 4 ^{to R 11} in each of the formulas (2). Further, the formula (2) 'in the X' ¹ and Definition preferred is the same as the X ¹ in each of the formulas (2).

In addition, when A ′ in Formula (5) or Formula (6) does not include the chemical structure of Formula (2) ′, any known chemical structure can be introduced into A ′.
M in said Formula (5) is an average value of the number of repetitions, and is 0 or more and 6 or less. When the bisphenol compound of formula (6) is reacted with epichlorohydrin by a known method, m is usually larger than 0. In order to set m to 0, an epoxy resin produced by a known method is highly purified by a technique such as distillation or crystallization, or after allylation of the bisphenol compound of the formula (6), There is a method of epoxidizing by oxidation. Thereby, the epoxy resin of this invention does not contain a secondary hydroxyl group, and can further improve a hygroscopic property and a dielectric characteristic. On the other hand, for example, when finely adjusting the adhesion to metal, the epoxy resin of the present invention is used within the range that does not significantly affect other physical properties such as hygroscopicity by using an appropriate m-number epoxy resin. An appropriate amount of secondary hydroxyl group can be present in the inside.

  In the bifunctional epoxy resin or diester compound used for the production of the epoxy resin of the present invention, the chemical structure represented by the formula (2) ′ has the entire A ′ in the formula (5) and the formula (6). It is preferable that 1-100 mol% is contained with respect to the number of moles. From the viewpoint of sufficiently expressing the heat resistance resulting from the chemical structure represented by the formula (2) ′, the chemical structure represented by the formula (2) ′ is more preferably 10 mol% or more, and still more preferably. Is at least 30 mol%, particularly preferably at least 50 mol%.

In the production of the epoxy resin of the present invention, the use amount of the above bifunctional epoxy resin and the diester compound is such that (epoxy group) :( ester group) = 1 to 1.2: 1 in the blending equivalent ratio thereof. Is preferable. It is preferable for this equivalent ratio to be in the above-mentioned range since it is easy to proceed with increasing the molecular weight in the state having an epoxy group at the molecular end.
Moreover, it is also possible to replace a part of the diester compound with the bisphenol compound represented by the formula (6). Thereby, as described above, the physical properties can be finely adjusted by making an appropriate amount of secondary hydroxyl group exist in the epoxy resin of the present invention.

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 the reaction between the epoxy group and the ester group. 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.

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 are preferable. 4- (dimethylamino) pyridine, 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0] nonene-5, 2-ethyl-4-methylimidazole Is 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 in the epoxy resin is preferably 2000 ppm or less, and the content of phosphorus in the epoxy resin is preferable because it may deteriorate the insulating characteristics or shorten the pot life of the composition. Is 2000 ppm or less. More preferably, the content of nitrogen in the epoxy resin is 1000 ppm or less, and the content of phosphorus in the epoxy resin is 1000 ppm or less.

  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 the glycol ether solvent 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 the epoxy resin, the polymerization reaction between the bifunctional epoxy resin and the diester 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 various additives such as other epoxy resins, inorganic fillers, coupling agents, antioxidants, and the like as necessary. The epoxy resin composition of the present invention is excellent in low moisture absorption, dielectric properties, heat resistance, and solvent resistance, and provides a cured product that sufficiently satisfies various physical properties required for various applications.

<Curing agent>
A curing agent can be blended with the epoxy resin of the present invention to obtain an epoxy resin composition. In this invention, 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 parts by weight with respect to 100 parts by weight of the solid content of the epoxy resin of the present invention. Further, it is more preferably 80 parts by weight or less, and still more preferably 60 parts by weight or less.
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 is 99/1 to 1/99. 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. The “total epoxy resin component” means the total of the epoxy resin of the present invention and other epoxy resins described later.

  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, imidazoles, active ester curing agents, and other usable curing agents are listed 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-cresol Novo Lac, xylenol novolac, 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, 2,6-dihydride Examples include xinaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, etc. .

  The phenolic curing agents mentioned above may be used alone or in a combination of two or more in any combination and ratio. Moreover, when a hardening | curing agent is a phenol type hardening | curing agent, it is preferable to use so that it may become the range of 0.8-1.5 by the equivalent ratio of the functional group in a hardening | curing agent with respect to the epoxy group in an epoxy resin. 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-based curing agent as the curing agent from the viewpoint of improving heat resistance and the like. Use of an amide type curing agent as the curing agent is preferable 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.

  The phenolic curing agents listed above may be used alone or in a combination of two or more in any combination and ratio. Moreover, it is preferable to use an amide type hardening | curing agent in 0.1-20 weight% with respect to the sum total of all the epoxy resin components and amide type hardening | curing agents as solid content in an epoxy resin composition.

[Imidazoles]
It is preferable to use imidazoles 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-tri Azine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and an epoxy resin and the above imidazoles Examples include adducts. 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. Moreover, it is preferable to use imidazole in 0.1-20 weight% with respect to the sum total of all the epoxy resin components and imidazoles as solid content in an epoxy resin composition.

[Active ester curing agent]
The use of an active ester curing agent as the curing agent is preferable from the viewpoint of reducing the water absorption 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.
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 curing agent to the epoxy group in all epoxy resins in the epoxy resin composition is in the range of 0.2 to 2.0. preferable.

[Other curing agents]
As a hardening | curing agent which can be used for the epoxy resin composition of this invention, as a thing other than a phenol type hardening | curing agent, an amide type hardening | curing agent, and imidazoles, for example, an amine hardening | curing agent (however, a tertiary amine is remove | excluded. ), Acid anhydride curing agents, tertiary amines, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing agents, block isocyanates Examples thereof include a curing agent. 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 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 amount of the other epoxy resin in the total epoxy resin component as a solid content is preferably 1% by weight or more. More preferably 5% by weight or more, still more preferably 10% by weight or more, on the other hand, preferably 99% by weight or less, more preferably 95% by weight or less, still more preferably 90% by weight or less. It is. 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 less than or equal to 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 film formability.

<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]
The cured product obtained by curing the epoxy resin of the present invention with a curing agent has an excellent balance of low moisture absorption, dielectric properties, heat resistance, chemical resistance (particularly solvent resistance), and exhibits good cured properties. is there. 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 progression 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 a method such as heating, decompression, and air drying, but the solvent is not more than 5% by mass in the resin semi-cured product. Also good.

[Use]
The epoxy resin of this invention is excellent in film forming property, and the epoxy resin composition containing this has the effect of giving the hardened | cured material excellent in chemical resistance (solvent resistance). 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 laminated board 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) Using the prepreg of (1) as a core material, a layer made of an epoxy resin composition and a conductive metal layer are laminated on it (one side or both sides) (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 and the conductive metal layer are alternately laminated to form 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 n The value of n 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) Film-forming property An epoxy resin or a solution of an epoxy resin composition was applied to a separator (silicone-treated polyethylene terephthalate film or Teflon (registered trademark) film) with an applicator, followed by 160 ° C. for 1.5 hours and then 200 ° C. And dried for 1.5 hours to evaluate whether a self-supporting film can be produced.
○: A self-supporting film is obtained, and there is sufficient flexibility. Δ: Flexibility is insufficient and somewhat fragile, but the film shape can be maintained. ×: The film shape is fragile and cannot be maintained / does not become a film.

5) Solvent resistance An epoxy resin film having a thickness of about 50 μm was obtained in the same manner as in 4). 100 g of tetrahydrofuran was put into a 200 ml sample bottle, a test piece obtained by cutting the obtained film into 4 cm × 4 cm was immersed, and left at room temperature for 12 hours or more, and the state was visually confirmed. Moreover, about what was able to maintain a film shape, it took out from tetrahydrofuran, and after drying at 100 degreeC for 2 hours, the weight was measured and the gel fraction was computed.
○: The film shape is not dispersed and the film shape can be maintained. Δ: Although the dispersion is observed, the film shape can be maintained. ×: The film shape cannot be maintained at all and is dispersed (gel fraction) = [{(Mass after drying with tetrahydrofuran and dried) − (Mass of test specimen before treatment)} / (Mass of test specimen before treatment)] × 100

[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)
(A-3): Mitsubishi Chemical Corporation product name “jER 806H” (bisphenol F type epoxy resin, epoxy equivalent 169 g / equivalent)
(A-4): Mitsubishi Chemical Corporation product name “jER YL6121H” (4,4′-biphenol type epoxy resin and 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol type epoxy) 1: 1 mixture of resins, epoxy equivalent 171 g / equivalent)
(A-5): Mitsubishi Chemical Corporation product name “jER YX7760” (epoxy equivalent 237 g / equivalent)
(A-6): Mitsubishi Chemical Corporation product name “jER YX7710” (epoxy equivalent 240 g / equivalent)

[Diester compounds]
(B-1): Diacetoxybiphenyl (B-2): Dibenzoyloxybiphenyl (B-3): 2,2-bis (4-acetoxyphenyl) propane
(B-4): 1,1-bis (4-acetoxyphenyl) -3,3,5-trimethylcyclohexane (B-5): 9,9-bis (4-acetoxyphenyl) fluorene

[Bisphenol compounds]
(P-1): 4,4 '-(fluorene-9,9-diyl) bis (2-methylphenol) (Honshu Chemical Co., Ltd. product name: BisOC-FL, hydroxyl group equivalent: 189 g / equivalent)

[catalyst]
(C-1): N, N′-dimethylaminopyridine (C-2): 2-ethyl-4 (5) -methylimidazole (product name: EMI24, manufactured by Mitsubishi Chemical Corporation), 50 wt% cyclohexanone solution ( C-3): Tetrabutylammonium bromide, 50% by weight aqueous solution

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

[Production and evaluation of epoxy resins: film-forming properties, solvent solubility]
<Examples 1-1 to 1-12, Comparative Example 1-1>
A bifunctional epoxy resin, a diester compound, a catalyst, and a reaction solvent are put in a reaction vessel equipped with a stirrer with the composition shown in Table 1, and the reaction time and reaction temperature shown in Table 1 are obtained under a nitrogen gas atmosphere. Reaction was performed. Then, the solvent for dilution was added and solid content concentration was adjusted. The results of analyzing the obtained resin are shown in Table 1.

<Comparative Example 1-2>
55. Product name “jER YX4000” (3,3 ′, 5,5′-tetramethyl-4,4′-biphenol diglycidyl ether, epoxy equivalent 186 g / equivalent) manufactured by Mitsubishi Chemical Corporation as a bifunctional epoxy resin. 0 g, 36.2 g of BPS-P (T) (bisphenol S, hydroxyl group equivalent 125 g / equivalent) as a diester compound, 0.47 g of a 27 mass% tetramethylammonium hydroxide aqueous solution as a catalyst, and cyclohexanone as a reaction solvent 74.6g was put into the reaction container with a stirrer, and it reacted at 145-155 degreeC by the nitrogen gas atmosphere for 5.5 hours. Thereafter, 138.2 g of cyclohexanone was added as a solvent for dilution to adjust the solid content concentration to 30% by mass. This high molecular weight epoxy resin had a number average molecular weight of 12,500 and a weight average molecular weight of 31,100. The acetic anhydride 32.9g was added here, keeping temperature at 60-80 degreeC, and it heated up at 120 degreeC and made it react for 2 hours. 50 g of cyclohexanone was added, and excess acetic anhydride and acetic acid produced by acylation were distilled off three times. Finally, after confirming that the distillate was almost neutral, the solid concentration was 30. It adjusted to the mass%. ^{As a result} of analysis by ¹ H-NMR, the acylation rate was 94.7%. On the other hand, the epoxy equivalent exceeded 140,000 g / equivalent, and it was found that substantially no epoxy group remained.

[Production and evaluation of epoxy resin composition / cured product: chemical resistance (solvent resistance)]
<Examples 2-1 to 2-12, Comparative Example 2-1>
The epoxy resin obtained in Examples 1-1 to 1-12 or the thermoplastic resin obtained in Comparative Example 1-2 and a phenol novolac resin 50 wt% MEK solution (trade name “PSM6200, manufactured by Gunei Chemical Co., Ltd.) )) And a 20 wt% MEK solution of 2-ethyl-4 (5) -methylimidazole (trade name “EMI24”, manufactured by Mitsubishi Chemical Corporation) as a curing accelerator, in a weight ratio (epoxy) The epoxy resin composition was obtained by mixing at a ratio of group: hydroxyl group = 1: 1). About these, chemical resistance (especially solvent resistance) was evaluated according to the above-mentioned method. The results are shown in Table-2.

From the results in Table 1, it can be seen that the epoxy resins of Examples 1-1 to 1-12 are excellent in film forming properties. Moreover, the epoxy resin of Examples 1-1 to 1-12 has an epoxy equivalent smaller than the number average molecular weight, and it is understood that one or more epoxy groups are contained in one molecule on average. On the other hand, Comparative Example 1-2 has almost no epoxy group at the end.
From the results shown in Table 2, in Examples 2-1 to 2-12, cured products obtained by adding a curing agent to the epoxy resins of Examples 1-1 to 1-12 and heating and curing them are resistant to chemicals (particularly resistance to chemicals). It can be seen that the solvent is excellent. Moreover, since the gel component remains, it is clear that the epoxy resins of Examples 1-1 to 1-12 are involved in the curing reaction, unlike Comparative Example 1-2 in which almost no epoxy group remains.

  From the above results, the epoxy resin of the present invention is superior in film forming properties as compared with the comparative example, and the epoxy resin composition containing the epoxy resin is a cured product excellent in chemical resistance (particularly solvent resistance). I know you give it.

  The epoxy resin of this invention is excellent in film forming property, and the epoxy resin composition containing this has the effect of giving the hardened | cured material excellent in chemical resistance (especially solvent resistance). 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 (11)

An epoxy resin represented by the following formula (1), having a weight average molecular weight of 5,000 to 200,000, an epoxy equivalent of 2,000 to 50,000 g / equivalent, and an epoxy equivalent of a number average molecular weight or less.

(In the above formula (1), A includes the chemical structure represented by the above formula (2), R ¹ and R ² may be different from each other, and may be a hydrogen atom or a chemistry represented by the above formula (3). And at least one of them is a group represented by the above formula (3), 5 mol% or more of R ³ is an aliphatic carbonyl group or aromatic carbonyl group having 1 to 10 carbon atoms, and the remainder is hydrogen. N is an average value of the number of repetitions and is from 5 to 500. In the above formula (2), X ¹ is a direct bond, a divalent hydrocarbon group having 1 to 13 carbon atoms, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ — and —CO—, each of R ^{4 to} R ¹¹ is independently a hydrogen atom or 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 alkeni having 1 to 12 carbon atoms And a group arbitrarily selected from a C 1-12 alkynyl group.) The epoxy resin of Claim 1 whose chemical structure represented by said Formula (2) is following formula (4) and / or following formula (5).

  An epoxy resin composition comprising the epoxy resin according to claim 1 and a curing agent. The curing agent is 0.1 to 100 solids with respect to 100 parts by weight of the solid content of the epoxy resin.
The epoxy resin composition of Claim 3 containing a weight part.   The epoxy resin composition according to claim 3 or 4, comprising the epoxy resin and another epoxy resin, wherein a weight ratio of the solid content of the epoxy resin and the other epoxy resin is 99/1 to 1/99. object.   The epoxy resin composition of Claim 5 which contains 0.1-100 weight part of said hardening | curing agents by solid content with respect to a total of 100 weight part of solid content of the said epoxy resin and another epoxy resin.   The epoxy resin composition according to any one of claims 3 to 6, wherein the curing agent is at least one selected from the group consisting of a phenolic curing agent, an amide curing agent, an imidazole, and an active ester curing agent. object.   Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claims 3 thru | or 7.   The laminated board for electric / electronic circuits which uses the epoxy resin composition of any one of Claims 3 thru | or 7. A bifunctional epoxy resin represented by the following formula (6) is reacted with a diester compound represented by the following formula (7) to give a weight average molecular weight of 5,000 to 200,000 and an epoxy equivalent of 2,000. The manufacturing method of the epoxy resin which obtains the epoxy resin of following formula (1) 'whose ˜50,000 g / equivalent and epoxy equivalent is the number average molecular weight or less.

(In the above formula (1) ′, A ′ includes the chemical structure represented by the above formula (2) ′, R ′ ¹ and R ′ ² may be different from each other, and may be a hydrogen atom or the above formula (3). And at least one of them is a group represented by the above formula (3) '. 5% by mole or more of R ′ ³ is an aliphatic carbonyl group or aromatic group having 1 to 10 carbon atoms. A group carbonyl group, the remainder being a hydrogen atom, and n is an average value of the number of repetitions and is 5 or more and 500 or less, In the formula (2) ′, X ′ ¹ is a direct bond, 2 having 1 to 13 carbon atoms. Is a group selected from a valent hydrocarbon group, —O—, —S—, —SO ₂ —, —C (CF ₃ ) ₂ — and —CO—, and 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, and 1 to 12 carbon atoms (It is a group arbitrarily selected from an alkenyl group and an alkynyl group having 1 to 12 carbon atoms.)

(In the formula (6) and / or (7), A 'is the above formula (2)' includes a chemical structure represented by, R ^'3 5 mole% or more aliphatic carbonyl having 1 to 10 carbon atoms A group or an aromatic carbonyl group, the remainder is a hydrogen atom, m is an average value of the number of repetitions, and is 0 or more and 6 or less.) The method for producing an epoxy resin according to claim 10, wherein the chemical structure represented by the formula (2) 'is the following formula (8) and / or the following formula (9).