JP2015134858A - Active ester resin, epoxy resin composition and cured product thereof, prepreg, circuit board, and build-up film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active ester resin which has low dielectric constant and dielectric loss tangent in a cured product, has excellent substrate adhesiveness and has high solvent solubility, an epoxy resin composition using the active ester resin as a curing agent and a cured product thereof, a prepreg, a circuit board, and a build-up film.SOLUTION: There is provided an active ester resin which is obtained by reacting a phenol compound having such a structure that a plurality of arylene groups are connected to each other through an aliphatic cyclic hydrocarbon group, aromatic nucleus-containing dicarboxylic acid or its halide, and an aromatic monohydroxy compound.

Description

  The present invention relates to an active ester resin having a low dielectric constant and dielectric loss tangent in a cured product, excellent substrate adhesion, and high solvent solubility, an epoxy resin composition using the same as a curing agent, a cured product thereof, and a prepreg. , Circuit board, and build-up film.

  Epoxy resin compositions containing an epoxy resin and a curing agent as an essential component exhibit excellent heat resistance and insulation in the cured product, and are widely used in electronic component applications such as semiconductors and multilayer printed boards. . Among the electronic component applications, in the technical field of insulating materials for multilayer printed circuit boards, resin materials having excellent dielectric properties that can cope with the increase in signal speed and frequency in various electronic devices, that is, dielectric constant and dielectric There is a demand for the development of a resin material having a sufficiently low tangent.

  As a material capable of realizing a low dielectric constant and a low dielectric loss tangent, a technique using an active ester compound obtained by esterifying dicyclopentadiene phenol resin and α-naphthol with isophthalic acid chloride as a curing agent for epoxy resin is known. (See Patent Document 1 below). The epoxy resin composition using the active ester compound described in Patent Document 1 obtains a cured product having a lower dielectric constant and dielectric loss tangent than when a conventional curing agent such as a phenol novolac resin is used. I can do it. However, the dielectric properties do not satisfy the recent required performance, and the adhesion to the substrate is not sufficient. Accordingly, there has been a demand for the development of an epoxy resin curing agent that has an even lower dielectric constant and dielectric loss tangent in the cured product and is excellent in substrate adhesion.

JP 2009-235165 A

  Therefore, the problem to be solved by the present invention is an active ester resin having both a low dielectric constant and a dielectric loss tangent in a cured product and excellent substrate adhesion, an epoxy resin composition using this as an curing agent, and its curing It is to provide an object, a prepreg, a circuit board, and a build-up film.

  As a result of intensive studies to solve the above problems, the present inventors have found that a structural unit (A) in which a plurality of arylene groups are knotted via an aliphatic cyclic hydrocarbon group is a naphthylene dicarbonyloxy group or a biphenylene dicarbonyloxy group. An active ester resin having a structural site linked to another structural unit (A), an arylene group, or an aryl group via a nodule group (B) containing two or more aromatic nuclei such as a group is very The inventors have found that a low dielectric constant and a dielectric loss tangent are exhibited and that the substrate adhesion is excellent, and the present invention has been completed.

  That is, in the present invention, the structural unit (A) in which a plurality of arylene groups are knotted via an aliphatic cyclic hydrocarbon group is represented by the following structural formulas (B-1) to (B-6).

（式中Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基の何れかであり、Ｘは炭素原子数２〜６の直鎖のアルキレン基、エーテル結合、カルボニル基、カルボニルオキシ基、スルフィド基、スルホン基の何れかであり、ｎ、ｐは１〜４の整数である。）
からなる群から選ばれる何れかの結節基（Ｂ）を介して他の構造ユニット（Ａ）、アリーレン基、又はアリール基と結節した構造部位を有することを特徴とする活性エステル樹脂に関する。

(Wherein R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and R ² is each independently carbon. It is any one of an alkyl group having 1 to 4 atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, and carbonyloxy. A group, a sulfide group, or a sulfone group, and n and p are integers of 1 to 4.)
The present invention relates to an active ester resin characterized by having a structural site linked to another structural unit (A), an arylene group, or an aryl group via any nodule group (B) selected from the group consisting of

  The present invention further relates to an epoxy resin composition containing the active ester resin.

  The present invention further relates to a cured product obtained by curing the epoxy resin composition.

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with a solution obtained by diluting the epoxy resin composition in an organic solvent and semi-curing the resulting impregnated substrate.

  The present invention further relates to a circuit board obtained by obtaining a varnish obtained by diluting the epoxy resin composition in an organic solvent, and heating and press-molding a varnish shaped into a plate shape and a copper foil.

  The present invention further relates to a build-up film obtained by applying a solution obtained by diluting the epoxy resin composition in an organic solvent on a base film and drying it.

  According to the present invention, an active ester resin having both a low dielectric constant and a dielectric loss tangent in a cured product and excellent substrate adhesion, an epoxy resin composition using the same as a curing agent, a cured product thereof, a prepreg, and a circuit board , And build-up films can be provided.

1 is a GPC chart of the active ester resin (1) obtained in Example 1. FIG. FIG. 2 is a GPC chart of the active ester resin (2) obtained in Example 2.

Hereinafter, the present invention will be described in detail.
In the novel active ester resin of the present invention, the structural unit (A) in which a plurality of arylene groups are knotted via an aliphatic cyclic hydrocarbon group has the following structural formulas (B-1) to (B-6).

（（式中Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基の何れかであり、Ｘは炭素原子数２〜６の直鎖のアルキレン基、エーテル結合、カルボニル基、カルボニルオキシ基、スルフィド基、スルホン基の何れかであり、ｎ、ｐは１〜４の整数である。）
からなる群から選ばれる何れかの結節基（Ｂ）を介して他の構造ユニット（Ａ）、アリーレン基、又はアリール基と結節した構造部位を有することを特徴とする。

(In the formula, each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group, and each R ² is independently It is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, and a carbonyl group. (It is either an oxy group, a sulfide group, or a sulfone group, and n and p are integers of 1 to 4.)
It has a structural site that is linked to another structural unit (A), an arylene group, or an aryl group via any nodule group (B) selected from the group consisting of:

  In the active ester resin of the present invention, the nodule group (B) is a so-called active ester group, and an ester residue derived from the nodule group (B) blocks the secondary hydroxyl group generated during the curing reaction with the epoxy resin. By doing so, the dielectric constant and dielectric loss tangent in the cured product can be reduced. The nodule group (B) is specifically a structural moiety represented by any one of the structural formulas (B-1) to (B-6), and these are structures having relatively high orientation. Therefore, in addition to exhibiting more excellent dielectric properties, it has a feature of excellent substrate adhesion, and for example, has a very high delamination strength when used for laminated plate applications.

  The structural unit (A) in which a plurality of arylene groups are knotted via an aliphatic cyclic hydrocarbon group of the active ester resin of the present invention includes, for example, an unsaturated aliphatic cyclic group containing two double bonds in one molecule. Examples include a structure obtained by polyaddition reaction of a hydrocarbon compound and a phenolic compound.

  The unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule includes, for example, dicyclopentadiene, cyclopentadiene multimer, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene. , Limonene, and the like. These may be used alone or in combination of two or more. Among these, dicyclopentadiene is preferable because a cured product having excellent heat resistance can be obtained. Since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain cyclopentadiene multimers or other aliphatic or aromatic diene compounds as impurities. However, in consideration of performance such as heat resistance, curability and moldability, it is desirable to use a product having a purity of 90% by mass or more of dicyclopentadiene.

  On the other hand, the phenolic compound is, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. You may use, and may use 2 or more types together. Among these, phenol is preferable because it becomes an active ester resin having high curability and excellent dielectric properties in a cured product.

  Therefore, the structural unit (A) has the following structural formula (A)

（式中、Ｒ^３はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、ｌは０又は１、ｍは１以上の整数である。）
で表される構造部位であることが好ましい。

(In the formula, each R ³ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group, and l is 0 or 1, m is an integer of 1 or more.)
It is preferable that it is a structure site | part represented by these.

  Specifically, the nodule group (B) of the active ester resin of the present invention is represented by the following structural formulas (B-1) to (B-6).

（式中Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基の何れかであり、Ｘは炭素原子数２〜６の直鎖のアルキレン基、エーテル結合、カルボニル基、カルボニルオキシ基、スルフィド基、スルホン基の何れかであり、ｎ、ｐは１〜４の整数である。）
の何れかで表される構造部位である。

(Wherein R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and R ² is each independently carbon. It is any one of an alkyl group having 1 to 4 atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, and carbonyloxy. A group, a sulfide group, or a sulfone group, and n and p are integers of 1 to 4.)
It is a structural part represented by either.

Among the structural parts represented by any one of the structural formulas (B-1) to (B-6), an active ester resin having excellent dielectric properties and substrate adhesion in a cured product is obtained. The structural site represented by (B-3) or (B-5) is preferable, and the structural site where X in the structural formula (B-3) is an ether bond, or in the structural formula (B-5), More preferably, the carbonyloxy group is a structural site in the 4,4′-position, and all R ^{1 in} each structural formula are preferably hydrogen atoms.

  In the active ester resin of the present invention, the structural unit (A) in which a plurality of arylene groups are linked through the aliphatic cyclic hydrocarbon group is converted into another structural unit (A), arylene through the linked group (B). Or a structural site linked to an aryl group.

  Examples of the arylene group include phenylene group, o-tolylene group, m-tolylene group, p-tolylene group, 3,5-xylylene group, o-biphenylene group, m-biphenylene group, p-biphenylene group, and 2-benzyl. Examples include phenylene group, 4-benzylphenylene group, 4- (α-cumyl) phenylene group, 1-naphthylene group, 2-naphthylene group and the like. Among these, a 1-naphthylene group or a 2-naphthylene group is preferable because a cured product having a low dielectric constant and dielectric loss tangent can be obtained.

  The aryl group includes, for example, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 3,5-xylyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 2 -Benzylphenyl group, 4-benzylphenyl group, 4- (α-cumyl) phenyl group, 1-naphthyl group, 2-naphthyl group and the like can be mentioned. Among these, a 1-naphthyl group or a 2-naphthyl group is preferable because a cured product having a low dielectric constant and dielectric loss tangent can be obtained.

  Since the active ester resin of the present invention has excellent dielectric properties in the cured product and high solvent solubility, the structural unit (A) in which a plurality of arylene groups are knotted through the aliphatic cyclic hydrocarbon group is provided. It is preferable that it is a thing which has a structure part knotted with another structural unit (A) or an aryl group through the said nodule group (B). That is, the active ester resin of the present invention has a structure in which the structural unit (A) is connected to another structural unit (A) via the nodule group (B) as a repeating unit, and an aryl group is connected to the terminal of the repeating unit. Those having a molecular structure are more preferred. When the structural unit (A) is [A], the dicarbonyloxy group (B) is [B], and the aryl group is [Ar], the following general formula (I)

で表すことが出来る。

It can be expressed as

  In the general formula (I), k represents an average value of repeating units, and becomes an active ester resin excellent in solvent solubility, and is preferably in the range of 0.25 to 3.5, preferably 0.75 to 3 More preferably, it is in the range of 0.0.

Here, the value of k of the active ester resin of the present invention represented by the general formula (I) can be determined as follows.
[How to find the value of k in general formula (2)]
Values of styrene equivalent molecular weight (α1, α2, α3, α4) corresponding to k = 1, k = 2, k = 3, k = 4, respectively, obtained by GPC measurement under the following conditions, and k = 1, k = 2, k = 3, k = 4 ratios (β1 / α1, β2 / α2, β3 / α3, β4 / α4) with the respective theoretical molecular weights (β1, β2, β3, β4) are obtained. / Α1 to β4 / α4) is determined. A value obtained by multiplying the number average molecular weight (Mn) obtained as a result of the GPC by this average value is used as an average molecular weight, and a value of k corresponding to the average molecular weight is calculated.

(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  Specifically, the active ester resin of the present invention described above can be represented by the following structural formula (1).

［式中、Ｂ’は下記構造式（Ｂ’−１）〜（Ｂ’−６）

[Wherein, B ′ represents the following structural formulas (B′-1) to (B′-6)

（式中Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基の何れかであり、Ｘは炭素原子数２〜６の直鎖のアルキレン基、エーテル結合、カルボニル基、カルボニルオキシ基、スルフィド基、スルホン基の何れかであり、ｎ，ｐは１〜４の整数である。）
からなる群から選ばれる何れかの構造部位であり、Ｒ^３はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｚはフェニル基、ナフチル基、又は、芳香核上に炭素原子数１〜４のアルキル基を１〜３個有するフェニル基或いはナフチル基であり、ｌは０又は１であり、ｋは繰り返し単位の平均で０．２５〜３．５である。］

(Wherein R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and R ² is each independently carbon. It is any one of an alkyl group having 1 to 4 atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, and carbonyloxy. A group, a sulfide group, or a sulfone group, and n and p are integers of 1 to 4.)
R ³ is independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group. Z is a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l is 0 or 1, k Is an average of repeating units of 0.25 to 3.5. ]

  Among the active ester resins represented by the structural formula (1), the following structural formula (1-1) is particularly preferable.

（式中、Ｒ^１及びＲ^３はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｚはフェニル基、ナフチル基、又は、芳香核上に炭素原子数１〜４のアルキル基を１〜３個有するフェニル基或いはナフチル基であり、ｌは０又は１であり、ｋは繰り返し単位の平均で０．２５〜３．５である。）
又は下記構造式（１−２）

(Wherein R ¹ and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and Z is phenyl A phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l is 0 or 1, and k is 0 on the average of repeating units. .25 to 3.5.)
Or the following structural formula (1-2)

（式中、Ｒ^１及びＲ^３はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｚはフェニル基、ナフチル基、又は、芳香核上に炭素原子数１〜４のアルキル基を１〜３個有するフェニル基或いはナフチル基であり、ｌは０又は１であり、ｋは繰り返し単位の平均で０．２５〜３．５である。）
で表される分子構造を有するものが挙げられる。

(Wherein R ¹ and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and Z is phenyl A phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l is 0 or 1, and k is 0 on the average of repeating units. .25 to 3.5.)
The thing which has the molecular structure represented by these is mentioned.

  The active ester resin of the present invention includes, for example, a phenolic compound (a) having a structure in which a plurality of aryl groups having a phenolic hydroxyl group are linked via an aliphatic cyclic hydrocarbon group, an aromatic nucleus-containing dicarboxylic acid, or a halide thereof. It can be produced by a method in which (b) is reacted with the aromatic monohydroxy compound (c).

  The phenolic compound (a) having a structure in which a plurality of aryl groups having a phenolic hydroxyl group are linked via the above-described aliphatic cyclic hydrocarbon group is, for example, unsaturated containing two double bonds in one molecule. Examples thereof include those obtained by polyaddition reaction of an aliphatic cyclic hydrocarbon compound and a phenolic compound.

  The unsaturated aliphatic cyclic hydrocarbon compound containing two double bonds in one molecule includes, for example, dicyclopentadiene, cyclopentadiene multimer, tetrahydroindene, 4-vinylcyclohexene, 5-vinyl-2-norbornene. , Limonene and the like, and each may be used alone or in combination of two or more. Among these, dicyclopentadiene is preferable because a cured product having excellent heat resistance can be obtained. Since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain cyclopentadiene multimers or other aliphatic or aromatic diene compounds as impurities. However, in consideration of performance such as heat resistance, curability and moldability, it is desirable to use a product having a purity of 90% by mass or more of dicyclopentadiene.

  On the other hand, the phenolic compound is, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol, chlorophenol, bromophenol, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. You may use, and may use 2 or more types together. Of these, phenol is preferred because it is an active ester resin having high curability and excellent dielectric properties in the cured product.

  Next, the aromatic nucleus-containing dicarboxylic acid or its halide (b) has the following structural formulas (b-1) to (b-6).

（式中、Ｒ^１はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、アラルキル基の何れかであり、Ｒ^２はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基の何れかである。また、式中Ｘは炭素原子数２〜６の直鎖のアルキレン基、エーテル結合、カルボニル基、カルボニルオキシ基、スルフィド基、スルホン基の何れかであり、Ｙはヒドロキシル基又はハロゲン原子を表し、ｎ、ｐは１〜４の整数である。）
の何れかで表される化合物である。

(In the formula, each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and each R ² is independently Any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, wherein X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, A carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group, Y represents a hydroxyl group or a halogen atom, and n and p are integers of 1 to 4.)
It is a compound represented by either.

Among the compounds represented by any one of the structural formulas (b-1) to (b-6), an active ester resin having excellent dielectric properties and substrate adhesion in a cured product is obtained. The compound represented by b-3) or (b-5) is preferred, and the compound in which X in the structural formula (b-3) is an ether bond, or two carbonyl groups in the structural formula (b-5) are A compound in the 4,4′-position is more preferable, and all R ^{1 in} each structural formula are preferably hydrogen atoms.

  The aromatic monohydroxy compound (c) is, for example, an alkylphenol such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol; o-phenylphenol, p-phenylphenol, 2-benzylphenol Aralkylphenols such as 4-benzylphenol and 4- (α-cumyl) phenol; naphthol compounds such as 1-naphthol and 2-naphthol. Among these, 1-naphthol or 2-naphthol is preferable because a cured product having a low dielectric constant and dielectric loss tangent can be obtained.

  The reaction between the phenolic compound (a), the aromatic nucleus-containing dicarboxylic acid or its halide (b), and the aromatic monohydroxy compound (c) is, for example, a temperature condition of 40 to 65 ° C. in the presence of an alkali catalyst. Can be done below. Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Among these, sodium hydroxide or potassium hydroxide is preferable because of high reaction efficiency. These catalysts may be used as a 3.0 to 30% aqueous solution.

  It is preferable to carry out the reaction in an organic solvent because the reaction can be easily controlled. Examples of the organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

  The reaction ratio of the phenolic compound (a), the aromatic nucleus-containing dicarboxylic acid or its halide (b), and the aromatic monohydroxy compound (c) can be appropriately returned according to the desired molecular design. Among them, since it becomes an active ester resin having better solvent solubility and high curability, the phenol is used with respect to a total of 1 mol of the carboxyl group or acid halide group of the aromatic nucleus-containing dicarboxylic acid or its halide (b). The phenolic hydroxyl group of the aromatic compound (a) is in the range of 0.25 to 0.90 mol, and the hydroxyl group of the aromatic monohydroxy compound (c) is in the range of 0.10 to 0.75 mol. It is preferable to use each raw material in such a ratio that the phenolic hydroxyl group of the phenolic compound (a) is in the range of 0.50 to 0.75 mol. Becomes, and the hydroxyl groups of the aromatic monohydroxy compound (c) has it is more preferable to use the raw materials so that the ratio of 0.25 to 0.50 mols.

  After completion of the reaction, if an aqueous solution is used as the alkali catalyst, the reaction solution is allowed to stand and remove to remove the aqueous layer, and the remaining organic layer is washed with water, and washed with water until the aqueous layer is almost neutral. By repeating the above, the desired active ester resin can be obtained.

  The active ester resin thus obtained has high solubility in various organic solvents and is excellent in substrate adhesion, so that its softening point is in the range of 60 to 170 ° C. preferable.

  In addition, the functional group equivalent of the active ester resin of the present invention is excellent in curability and has a low dielectric constant and preferential tangent when the total number of arylcarbonyloxy groups and phenolic hydroxyl groups in the resin structure is the number of functional groups of the resin. Since a cured product is obtained, 220 to 360 g / eq. It is preferable that it is the range of 240-320 g / eq. More preferably, it is the range.

  The epoxy resin composition of this invention contains the above-mentioned active ester resin and an epoxy resin as an essential component.

  Examples of the epoxy resin used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type. Epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol Condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic tree Type epoxy resins, biphenyl-modified novolak type epoxy resins. Among these epoxy resins, tetramethylbiphenol type epoxy resin, biphenyl aralkyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, and novolac type epoxy resin are used in that a cured product having excellent flame retardancy can be obtained. A dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties is obtained.

  In the epoxy resin composition of the present invention, the compounding amount of the active ester resin and the epoxy resin is excellent in curability and a cured product having a low dielectric constant and dielectric loss tangent is obtained. It is preferable that the epoxy group in the epoxy resin has a ratio of 0.8 to 1.2 equivalents with respect to 1 equivalent in total. Here, the active group in the active ester resin refers to an arylcarbonyloxy group and a phenolic hydroxyl group in the resin structure.

In the epoxy resin composition of this invention, you may use together an above described active ester resin and another hardening | curing agent. Other curing agents used here are, for example, amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, guanidine derivatives: dicyandiamide, linolenic acid 2 Amide compounds such as polyamide resin synthesized from a monomer and ethylenediamine: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, Acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride: phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclope Tadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (Polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl modified naphthol resin (polyvalent naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine modified phenolic resin (melamine or benzoguanamine etc. And polyhydric phenol compounds such as linked polyhydric phenol compounds).

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are preferable because they have excellent dielectric properties and moisture absorption resistance. Specifically, phenol novolac resins, cresol novolak resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins Phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenol resin are preferable.

  When the other curing agents described above are used in combination, the amount used is preferably in the range of 10 to 50 parts by mass in a total of 100 parts by mass of the active ester resin and the other curing agent.

  The epoxy resin composition of the present invention may contain a curing accelerator as necessary. Examples of the curing accelerator used here include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In particular, when the epoxy resin composition of the present invention is used as a build-up material application or a circuit board application, dimethylaminopyridine and imidazole are preferable because of excellent heat resistance, dielectric characteristics, solder resistance, and the like.

  In addition, as described above, the active ester resin of the present invention is characterized by expressing excellent solvent solubility, and when the epoxy resin composition of the present invention is used for build-up material applications or circuit board applications, Instead of the solvent such as toluene that has been used, it can be varnished using an alcohol solvent or an ester solvent. Organic solvents that can be used as the solvent of the epoxy resin composition of the present invention include conventionally used aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, Cellulose acetate, propylene glycol monomethyl ether acetate, acetate solvents such as carbitol acetate, alcohol solvents such as ethanol, propanol, butanol, carbitol solvents such as cellosolve, butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. Is mentioned.

  When the epoxy resin composition of the present invention is used for printed wiring board applications, it is preferably a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc., and has a nonvolatile content of 40 to 80 It is preferable to use at a ratio of mass%. On the other hand, for use in build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethanol, propanol It is preferable to use an alcohol solvent such as butanol, a carbitol solvent such as cellosolve or butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and a non-volatile content of 30 to 60% by mass. preferable.

  Moreover, the epoxy resin composition of this invention may use together other thermosetting resin suitably as needed. Examples of other thermosetting resins that can be used here include cyanate ester compounds, vinylbenzyl compounds, acrylic compounds, maleimide compounds, and copolymers of styrene and maleic anhydride. When other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as the effect of the present invention is not impaired, but is in the range of 1 to 50 parts by weight in 100 parts by weight of the epoxy resin composition. It is preferable.

  When the active ester resin of the present invention is used for applications requiring higher flame retardancy than for printed wiring boards, a non-halogen flame retardant containing substantially no halogen atoms may be blended.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Examples thereof include cyclic organic phosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  For example, in the case where red phosphorus is used in 100 parts by mass of the epoxy resin composition, the amount of these phosphorus-based flame retardants is preferably 0.1 to 2.0 parts by mass. When using, it is preferable to mix | blend in the range of 0.1-10.0 mass part, and it is more preferable to mix | blend in the range of 0.5-6.0 mass part.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, sulfuric acid such as guanylmelamine sulfate, melem sulfate, melam sulfate Examples thereof include aminotriazine compounds, aminotriazine-modified phenol resins, and aminotriazine-modified phenol resins that are further modified with tung oil, isomerized linseed oil, and the like.

  Examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The blending amount of the nitrogen-based flame retardant is preferably blended in the range of 0.05 to 10 parts by weight, for example, in the range of 0.1 to 5 parts by weight in 100 parts by weight of the epoxy resin composition. Is more preferable.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  It is preferable to mix | blend the compounding quantity of the said silicone type flame retardant in the range of 0.05-20 mass parts in 100 mass parts of epoxy resin compositions, for example. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

  Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Examples of the low-melting-point glass include Sheepley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O. Glass forms such as _5- B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. A compound can be mentioned.

  The blending amount of the inorganic flame retardant is, for example, preferably in the range of 0.05 to 20 parts by mass and in the range of 0.5 to 15 parts by mass in 100 parts by mass of the epoxy resin composition. Is more preferable.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. And the like.

  It is preferable to mix | blend the compounding quantity of the said organometallic salt type flame retardant in the range of 0.005-10 mass parts in 100 mass parts of epoxy resin compositions, for example.

  The epoxy resin composition of this invention can mix | blend an inorganic filler as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total amount of the thermosetting resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  In addition to the above, the epoxy resin composition of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

  The epoxy resin composition of the present invention is obtained by uniformly mixing the above-described components, and can be easily made into a cured product by a method similar to the curing of conventionally known epoxy resin compositions. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Since the epoxy resin composition of the present invention has a low dielectric constant and dielectric loss tangent of the cured product, circuit boards such as hard printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulation materials for build-up boards, etc. It can be suitably used for various electronic materials such as insulating materials for semiconductors, semiconductor sealing materials, conductive pastes, build-up adhesive films, resin casting materials, adhesives and the like. Especially, taking advantage of the high solubility of the active ester resin of the present invention in various organic solvents, especially for circuit board materials such as hard printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulation materials for build-up boards. It can be preferably used.

  Of these, when applied to circuit board applications, a varnish obtained by diluting the epoxy resin composition of the present invention in an organic solvent is obtained, and this is formed into a plate shape, laminated with copper foil, and heated and pressed. Can be manufactured. In addition, when applying to hard printed circuit board applications, a prepreg is obtained by impregnating a reinforcing base material with a varnish-like epoxy resin composition containing an organic solvent and semi-curing it, and copper foil is laminated on it and heated. It can be manufactured by a method of pressure bonding. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, the varnish-like epoxy resin composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. to obtain a prepreg that is a cured product. . Under the present circumstances, although the mass ratio of the thermosetting resin composition to be used and a reinforcement base material is not specifically limited, Usually, it is preferable to prepare so that the resin content in a prepreg may be 20-60 mass%. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours, A target circuit board can be obtained.

  In order to produce a flexible wiring board from the epoxy resin composition of the present invention, an epoxy resin composition containing an organic solvent is applied to an electrically insulating film using a coating machine such as a reverse roll coater or a comma coater. Subsequently, it heats for 1 to 15 minutes at 60-170 degreeC using a heater, volatilizes a solvent, and makes an epoxy resin composition B-stage. Next, the metal foil is thermocompression bonded to the resin composition layer using a heating roll or the like. At that time, the pressure is preferably 2 to 200 N / cm and the pressure is preferably 40 to 200 ° C. If sufficient adhesive performance can be obtained, the process may be completed here. However, when complete curing is required, it is preferably post-cured at 100 to 200 ° C. for 1 to 24 hours. The thickness of the resin composition layer after finally curing is preferably in the range of 5 to 100 μm.

  In order to produce an interlayer insulating material for a build-up board from the epoxy resin composition of the present invention, for example, an epoxy resin composition appropriately blended with rubber, filler or the like is applied to a wiring board on which a circuit is formed by a spray coating method or curtain coating. After applying using a method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. Also, a copper foil with resin obtained by semi-curing the resin composition on the copper foil is heat-pressed at 170 to 250 ° C. on a wiring board on which a circuit is formed, thereby forming a roughened surface and a plating process. It is also possible to produce a build-up board without the above.

  The method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, an adhesive for multilayer printed wiring boards by applying the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of using a film is mentioned.

  When the epoxy resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film and further heating, or It can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of an epoxy resin composition.

  The thickness of the formed layer (α) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the said layer ((alpha)) may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The above support film is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (α) is protected with a protective film, Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so that α) is in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  When the epoxy resin composition of the present invention is used as a conductive paste, for example, a method in which fine conductive particles are dispersed in an epoxy resin composition to form a composition for an anisotropic conductive film, a circuit that is liquid at room temperature Examples thereof include a paste resin composition for connection and an anisotropic conductive adhesive.

  The epoxy resin composition of the present invention can also be used as a resist ink. In this case, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are blended in the epoxy resin composition, and further a pigment, talc, and filler are added to obtain a resist ink composition. Then, after apply | coating on a printed circuit board by a screen printing system, the method of setting it as a resist ink hardened | cured material is mentioned.

  As described above, since the active ester resin of the present invention has higher solvent solubility compared to conventional active ester resins, it can be easily varnished when applied to the various electronic material applications. In place of the conventionally mainstream solvents such as toluene, which have a high environmental load, organic solvents having a lower environmental load such as ester solvents and alcohol solvents can be used. Moreover, since the cured product of the epoxy resin composition of the present invention has a characteristic that both the dielectric constant and the dielectric loss tangent are low, it can contribute to the realization of the high-speed operation speed of the high-frequency device.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. The softening point measurement, toluene solution viscosity, GPC measurement, ¹³ C-NMR, and MALDI-MS spectrum were measured under the following conditions.

Softening point measurement method: compliant with JIS K7234.

Toluene solution viscosity: Conforms to JIS Z8803.

GPC: Measured under the following conditions.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Example 1 Production of Active Ester Resin (1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, stirrer, 295.1 g of 4,4′-oxybisbenzoyl chloride (moles of acid chloride group) Number: 2.0 mol) and 1338 g of toluene were charged, and the inside of the system was dissolved under reduced pressure nitrogen. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g of dicyclopentadiene phenol resin (the number of moles of phenolic hydroxyl group: 1.33 mol) were charged, and the system was dissolved by substituting with nitrogen under reduced pressure. It was. Thereafter, while purging with nitrogen gas, the inside of the system was controlled to 60 ° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester resin (1) in a toluene solution state having a nonvolatile content of 65%. The solution viscosity of the toluene solution having a nonvolatile content of 65% by mass was 14870 mPa · S (25 ° C.). Moreover, the softening point of active content (1) solid content obtained by drying this was 174 degreeC. A GPC chart of the active ester resin (1) is shown in FIG.

Example 2 Production of Active Ester Resin (2) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 279.1 g of biphenyl-4,4′-dicarboxylic acid dichloride (of acid chloride group) Mole number: 2.0 mol) and 1338 g of toluene were charged, and the inside of the system was purged with nitrogen under reduced pressure to be dissolved. Next, 96.5 g (0.67 mol) of α-naphthol and 219.5 g of dicyclopentadiene phenol resin (the number of moles of phenolic hydroxyl group: 1.33 mol) were charged, and the system was dissolved by substituting with nitrogen under reduced pressure. It was. Thereafter, while purging with nitrogen gas, the inside of the system was controlled to 60 ° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester resin (2) in a toluene solution state having a nonvolatile content of 65%. The solution viscosity of the toluene solution having a nonvolatile content of 65% by mass was 5540 mPa · S (25 ° C.). Moreover, the softening point of solid content of active ester resin (2) obtained by drying this was 138 degreeC. A GPC chart of the active ester resin (2) is shown in FIG.

Comparative Production Example 1 Production of Active Ester Resin (1 ') A flask equipped with a thermometer, dropping funnel, condenser, fractionator, stirrer and isophthalic acid chloride (203.0 g (1.0 mol) and dimethylformamide 1254 g Then, 288.0 g (2.0 mol) of α-naphthol was charged and the system was purged with nitrogen under reduced pressure, and then purged with nitrogen gas, The inside of the system was controlled to 60 ° C. or less, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and stirring was continued for 1.0 hour under these conditions. Further, the water phase was removed, and water was added to the toluene phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was allowed to stand and removed to remove the aqueous layer. Repeat operation Thereafter, water was removed by decanter dehydration to synthesize an active ester resin (1 ′) in a dimethylformamide solution having a nonvolatile content of 65%, and the solution viscosity of the toluene solution having a nonvolatile content of 65% by mass was 860 mPa · S (25 ° C. )Met.

Comparative Synthesis Example 2 Production of Active Ester Resin (2 ′) 203.0 g of isophthalic acid chloride (number of moles of acid chloride group: 2.0) in a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer Mol) and 1800 g of toluene were charged and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Next, 57.6 g (0.4 mol) of α-naphthol and 412.5 g of dicyclopentadiene phenol resin (mole number of phenolic hydroxyl group: 2.5 mol) were charged, and the inside of the system was purged with nitrogen under reduced pressure and dissolved. Thereafter, while purging with nitrogen gas, the inside of the system was controlled to 60 ° C. or lower, and 400 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the toluene phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by decanter dehydration to obtain an active ester resin (2 ′) in a toluene solution state having a nonvolatile content of 65% by mass. The resulting active ester resin (2 ′) had a softening point after drying of 184 ° C.

<Preparation of epoxy resin composition and evaluation of physical properties>
In accordance with the composition shown in Table 1 below, as an epoxy resin, HP-7200H manufactured by DIC (dicyclopentadiene phenol type epoxy resin, melt viscosity at 150 ° C., 0.30 poise, epoxy group equivalent 277 g / equivalent), and curing agent (1 ), (2), (1 ′), and (2 ′) are added, and an amount of 0.5 phr dimethylaminopyridine is added as a curing catalyst, and finally the nonvolatile content (N.V. ) Was adjusted by blending methyl ethyl ketone so as to be 58% by mass.
Next, a laminate was prepared by curing under the following conditions, and heat resistance, dielectric properties and flame retardancy were evaluated by the following methods. The results are shown in Table 1.

<Laminate production conditions>
Base material: Glass cloth “# 2116” (210 × 280 mm) manufactured by Nitto Boseki Co., Ltd.
Number of plies: 6 Condition of prepreg: 160 ° C
Curing conditions: 200 ° C., 40 kg / cm ² for 1.5 hours, post-molding plate thickness: 0.8 mm

<Measurement of dielectric constant and dissipation factor>
In accordance with JIS-C-6481, the dielectric at 1 GHz of the test piece after being stored in a room at 23 ° C. and 50% humidity for 24 hours after being completely dried by an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. The rate and dielectric loss tangent were measured.

<Adhesion (delamination strength)>
Interlaminar peel strength: evaluated according to JIS-K6481.

table 1

Claims (10)

The structural unit (A) in which a plurality of arylene groups are knotted via an aliphatic cyclic hydrocarbon group has the following structural formulas (B-1) to (B-6)

(Wherein R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and R ² is each independently carbon. It is any one of an alkyl group having 1 to 4 atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, and carbonyloxy. A group, a sulfide group, or a sulfone group, and n and p are integers of 1 to 4.)
An active ester resin characterized by having a structural site linked to another structural unit (A), an arylene group, or an aryl group via any nodule group (B) selected from the group consisting of A phenolic compound (a) having a structure in which a plurality of aryl groups having a phenolic hydroxyl group are linked via an aliphatic cyclic hydrocarbon group, an aromatic nucleus-containing dicarboxylic acid or its halide (b), and an aromatic monohydroxy compound The phenolic hydroxyl group of the phenolic compound (a) is 0.25 to 0 with respect to 1 mol in total of the carboxyl group or acid halide group of the aromatic nucleus-containing dicarboxylic acid or its halide (b). Obtained by reacting at a ratio such that the hydroxyl group of the aromatic monohydroxy compound (c) is in the range of 0.10 to 0.75 mol, and the aromatic nucleus-containing dicarboxylic acid or The halide (b) is represented by the following structural formulas (b-1) to (b-6).

(In the formula, each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and each R ² is independently Any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, wherein X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, A carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group, Y represents a hydroxyl group or a halogen atom, and n and p are integers of 1 to 4.)
The active ester resin according to claim 1, which is a compound represented by any one of: The structural unit (A) in which a plurality of arylene groups are knotted via the aliphatic cyclic hydrocarbon group has the following structural formula (A)

(In the formula, each R ³ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group, and l is 0 or 1, m is an integer of 1 or more.)
The active ester resin according to claim 2, which is a structural moiety represented by the formula: The following structural formula (1)

[Wherein, B ′ represents the following structural formulas (B′-1) to (B′-6)

(Wherein R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and R ² is each independently carbon. It is any one of an alkyl group having 1 to 4 atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group, and X is a linear alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, and carbonyloxy. A group, a sulfide group, or a sulfone group, and n and p are integers of 1 to 4.)
R ³ is independently any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and an aralkyl group. Z is a phenyl group, a naphthyl group, or a phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l is 0 or 1, k Is an average of repeating units of 0.25 to 3.5. ]
The active ester resin of Claim 3 which has the molecular structure represented by these. The following structural formula (1-1)

(Wherein R ¹ and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and Z is phenyl A phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l is 0 or 1, and k is 0 on the average of repeating units. .25 to 3.5.)
Or the following structural formula (1-2)

(Wherein R ¹ and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an aralkyl group, and Z is phenyl A phenyl group or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, l is 0 or 1, and k is 0 on the average of repeating units. .25 to 3.5.)
The active ester resin of Claim 4 which has the molecular structure represented by these. An epoxy resin composition comprising an epoxy resin and an active ester resin as essential components, wherein the active ester resin according to any one of claims 1 to 5 is used as the active ester resin. A cured product obtained by curing the epoxy resin composition according to claim 6. A prepreg obtained by impregnating a reinforcing base material with the epoxy resin composition according to claim 6 diluted in an organic solvent, and semi-curing the resulting impregnated base material. A circuit board obtained by obtaining a varnish obtained by diluting the epoxy resin composition according to claim 6 in an organic solvent, and subjecting the varnish to a plate shape and a copper foil. The buildup film obtained by apply | coating what dried the epoxy resin composition of Claim 6 in the organic solvent on a base film, and making it dry.

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