JP6278239B2 - Active ester resin, epoxy resin composition, cured product thereof, prepreg, circuit board, and build-up film - Google Patents

Description

  The present invention relates to an active ester resin having a low dielectric constant and dielectric loss tangent in a cured product and excellent in all of heat resistance, moisture absorption resistance, and thermal conductivity, an epoxy resin composition using this as an curing agent, and the cured product , 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 resin obtained by esterifying dicyclopentadiene phenol resin and α-naphthol with isophthalic acid chloride as an epoxy resin curing agent is known. (See Patent Document 1 below). The epoxy resin composition using the active ester resin 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 other properties such as heat resistance, moisture absorption resistance and thermal conductivity have not been 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 that is excellent in all of heat resistance, moisture absorption resistance, and thermal conductivity.

JP 2009-235165 A

  Therefore, the problem to be solved by the present invention is an active ester resin having a low dielectric constant and dielectric loss tangent in a cured product and excellent in all of heat resistance, moisture absorption resistance, and thermal conductivity, and a curing agent. An object of the present invention is to provide an epoxy resin composition, a cured product thereof, a prepreg, a circuit board, and a buildup film.

  As a result of intensive studies to solve the above problems, the present inventors have found that the following structural formula (1)

［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、アリール基、アラルキル基の何れかであり、ｍは１〜３の整数である。Ｘはそれぞれ独立に下記構造式（Ｘ−１）〜（Ｘ−３）

[Wherein 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, an aryl group or an aralkyl group, and m is an integer of 1 to 3 It is. X is each independently the following structural formulas (X-1) to (X-3)

（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、アリール基、アラルキル基の何れかであり、ｌは１〜３の整数である。Ｙは炭素原子数２〜６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る。］
の何れかで表される構造部位である。ｎは繰り返し単位数を表し０又は１以上の整数である。］
で表されるフェノール性水酸基含有樹脂（Ａ）を用いて得られる活性エステル樹脂は、その硬化物において非常に低い誘電率と誘電正接とを示し、かつ、耐熱性、耐吸湿性、及び熱伝導性の何れにも優れることを見出し、本発明を完成するに至った。

(Wherein 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, an aryl group, or an aralkyl group, and l is an integer of 1 to 3) Y is any one of an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, and a sulfone group.
It is a structural part represented by either. n represents the number of repeating units and is 0 or an integer of 1 or more. ]
The active ester resin obtained using the phenolic hydroxyl group-containing resin (A) represented by the formula shows a very low dielectric constant and dielectric loss tangent in the cured product, and has heat resistance, moisture absorption resistance, and heat conduction. As a result, the present invention was completed.

  That is, the present invention provides the following structural formula (1)

［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、アリール基、アラルキル基の何れかであり、ｍは１〜３の整数である。Ｘはそれぞれ独立に下記構造式（Ｘ−１）〜（Ｘ−３）

[Wherein 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, an aryl group or an aralkyl group, and m is an integer of 1 to 3 It is. X is each independently the following structural formulas (X-1) to (X-3)

（式中Ｒ^２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、アリール基、アラルキル基の何れかであり、ｌは１〜３の整数である。Ｙは炭素原子数２〜６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る。］
の何れかで表される構造部位である。ｎは繰り返し単位数を表し０又は１以上の整数である。］
で表されるフェノール性水酸基含有樹脂（Ａ）、芳香族二塩基酸又はそのハライド（Ｂ）、及び芳香族モノヒドロキシ化合物（Ｃ）を反応させて得られる分子構造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 ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l is an integer of 1 to 3) Y is any one of an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, and a sulfone group.
It is a structural part represented by either. n represents the number of repeating units and is 0 or an integer of 1 or more. ]
An activity characterized by having a molecular structure obtained by reacting a phenolic hydroxyl group-containing resin (A), an aromatic dibasic acid or its halide (B), and an aromatic monohydroxy compound (C) represented by It relates to an ester resin.

  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 a low dielectric constant and dielectric loss tangent in a cured product and excellent in all of heat resistance, moisture absorption resistance, and thermal conductivity, an epoxy resin composition using the same as a curing agent, Hardened | cured material, a prepreg, a circuit board, and a buildup film 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.
The active ester resin of the present invention has the following structural formula (1)

［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、アリール基、アラルキル基の何れかであり、ｍは１〜３の整数である。Ｘはそれぞれ独立に下記構造式（Ｘ−１）〜（Ｘ−３）

[Wherein 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, an aryl group or an aralkyl group, and m is an integer of 1 to 3 It is. X is each independently the following structural formulas (X-1) to (X-3)

（式中Ｒ^２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、アリール基、アラルキル基の何れかであり、ｌは１〜３の整数である。Ｙは炭素原子数２〜６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る。］
の何れかで表される構造部位である。ｎは繰り返し単位数を表し０又は１以上の整数である。］
で表されるフェノール性水酸基含有樹脂（Ａ）、芳香族二塩基酸又はそのハライド（Ｂ）、及び芳香族モノヒドロキシ化合物（Ｃ）を反応させて得られる分子構造を有することを特徴とする。

(Wherein R ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l is an integer of 1 to 3) Y is any one of an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, and a sulfone group.
It is a structural part represented by either. n represents the number of repeating units and is 0 or an integer of 1 or more. ]
It is characterized by having a molecular structure obtained by reacting a phenolic hydroxyl group-containing resin (A), an aromatic dibasic acid or its halide (B), and an aromatic monohydroxy compound (C) represented by the formula:

  The ester bond site generated by the reaction of the phenolic hydroxyl group-containing resin (A), the aromatic dibasic acid or its halide (B), and the aromatic monohydroxy compound (C) is a so-called active ester group. By blocking the secondary hydroxyl group generated during the curing reaction with the ester residue derived from the active ester group, the dielectric constant and dielectric loss tangent of the cured product can be reduced. X in the structural formula (1) representing the phenolic hydroxyl group-containing resin (A) is specifically a structural site represented by any one of the structural formulas (X-1) to (X-3). Since these are structures with relatively high orientation, in addition to exhibiting more excellent dielectric properties, they have characteristics of excellent heat resistance, moisture absorption resistance, and thermal conductivity.

  X in the structural formula (1) represents the following structural formulas (X-1) to (X-3).

（式中Ｒ^２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、アリール基、アラルキル基の何れかであり、ｌは１〜３の整数である。Ｙは炭素原子数２〜６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る。］
の何れかで表される構造部位である。

(Wherein R ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l is an integer of 1 to 3) Y is any one of an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, and a sulfone group.
It is a structural part represented by either.

R ² in the formula is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, specifically, a methyl group Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group and t-butyl group; alkoxy groups such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group and t-butoxy group; phenyl group , A naphthyl group, and an aryl group substituted with the alkyl group or alkoxy group on the aromatic nucleus; a phenylmethyl group, a naphthylmethyl group, an aralkyl group substituted with the alkyl group or alkoxy group on the aromatic nucleus, or the like Is mentioned. Among them, heat resistance and moisture resistance in the cured product, since the active ester resin excellent in dielectric properties, it is preferred that R ² is a hydrogen atom.

  Among the structural formulas (X-1) to (X-3), since it becomes an active ester resin excellent in heat resistance, moisture absorption resistance and thermal conductivity in the cured product, (X-1) or (X-2) It is preferable that it is a structural part represented by. That is, the phenolic hydroxyl group-containing resin (A) used in the present invention has the following structural formula (1-1) or (1-2).

（式中Ｒ^１、Ｒ^２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、アリール基、アラルキル基の何れかであり、ｌ、ｍはそれぞれ独立に１〜３の整数である。ｎは繰り返し単位数を表し０又は１以上の整数である。）
で表される分子構造を有することが好ましい。

(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l and m are Each independently represents an integer of 1 to 3. n represents the number of repeating units and is 0 or an integer of 1 or more.)
It preferably has a molecular structure represented by

R ¹ in the structural formula (1) 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, an aryl group, and an aralkyl group. And alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group; methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, t-butoxy group, etc. An alkoxy group; a phenyl group, a naphthyl group, and an aryl group in which the alkyl group or alkoxy group is substituted on the aromatic nucleus; a phenylmethyl group, a naphthylmethyl group, or the alkyl group or alkoxy group on the aromatic nucleus; Examples include substituted aralkyl groups. Among them, heat resistance and moisture resistance in the cured product, since the active ester resin excellent in dielectric properties, it is preferred that R ¹ is a hydrogen atom.

  N in the structural formula (1) represents the number of repeating units and is 0 or an integer of 1 or more. Especially, since the hardened | cured material which is more excellent in heat resistance is obtained, the said phenolic hydroxyl group containing resin (A) uses the bifunctional body ((alpha)) whose n value is 0 in the said Structural formula (1) in GPC measurement. It is preferably contained in an area ratio of 40% or more, more preferably 60% or more, even more preferably 70% or more, and particularly preferably 80% or more.

  In addition, in this invention, content of the bifunctional body ((alpha)) in the said phenolic hydroxyl group containing resin (A) is calculated from the GPC chart figure measured on the following conditions, The phenolic hydroxyl group containing resin (A) whole The ratio of the peak area corresponding to the bifunctional compound (α) to the peak area.

(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).

  The active ester resin of the present invention has the following structural formula (1)

［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、アリール基、アラルキル基の何れかであり、ｍは１〜３の整数である。Ｘはそれぞれ独立に下記構造式（Ｘ−１）〜（Ｘ−３）

[Wherein 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, an aryl group or an aralkyl group, and m is an integer of 1 to 3 It is. X is each independently the following structural formulas (X-1) to (X-3)

（式中Ｒ^２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、アリール基、アラルキル基の何れかであり、ｌは１〜３の整数であるＹは炭素原子数２〜６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る。］
の何れかで表される構造部位である。ｎは繰り返し単位数を表し０又は１以上の整数である。］
で表されるフェノール性水酸基含有樹脂（Ａ）、芳香族二塩基酸又はそのハライド（Ｂ）、及び芳香族モノヒドロキシ化合物（Ｃ）を反応させることにより製造することができる。

(Wherein R ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l is an integer of 1 to 3) Y is an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group.
It is a structural part represented by either. n represents the number of repeating units and is 0 or an integer of 1 or more. ]
It can manufacture by making the phenolic hydroxyl group containing resin (A) represented by these, an aromatic dibasic acid or its halide (B), and an aromatic monohydroxy compound (C) react.

  The phenolic hydroxyl group-containing resin (A) is, for example, the following structural formula (2)

（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、アリール基、アラルキル基の何れかであり、ｍは１〜３の整数である。）
で表されるフェノール化合物（ａ１）と、下記構造式（３−１）〜（３−３）

(Wherein 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, an aryl group, or an aralkyl group, and m is an integer of 1 to 3) .)
And a phenol compound (a1) represented by the following structural formulas (3-1) to (3-3):

（式中Ｒ^２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、アリール基、アラルキル基の何れかであり、ｌは１〜３の整数である。Ｙは炭素原子数２〜６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る。Ｚはハロゲン原子又はアルキルエーテル構造部位である。）
の何れかで表される芳香族化合物（ａ２）との反応により得ることができる。前記フェノール化合物（ａ１）や前記芳香族化合物（ａ２）は、それぞれ単独で用いても良いし、２種類以上を併用しても良い。

(Wherein R ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l is an integer of 1 to 3) Y is any one of an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, and a sulfone group, and Z is a halogen atom or an alkyl ether structure site.)
It can obtain by reaction with the aromatic compound (a2) represented by either. The phenol compound (a1) and the aromatic compound (a2) may be used alone or in combination of two or more.

R ¹ in the structural formula (2) has the same meaning as R ¹ in the structural formula (1). Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl An alkyl group such as a group; an alkoxy group such as a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, or a t-butoxy group; a phenyl group, a naphthyl group, and the alkyl group or alkoxy on the aromatic nucleus thereof. An aryl group substituted with a group; a phenylmethyl group, a naphthylmethyl group, and an aralkyl group substituted with the alkyl group or alkoxy group on the aromatic nucleus thereof; Among them, heat resistance and moisture resistance in the cured product, since the active ester resin excellent in dielectric properties, it is preferred that R ¹ is a hydrogen atom.

^{R 2} of the structural formula (3-1) to (3-3) in the above structural formula (X-1) ~ (X -3) in the same meaning as ^{R 2,} and specifically, a methyl group Alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group and t-butyl group; alkoxy groups such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group and t-butoxy group; phenyl group , A naphthyl group, and an aryl group substituted with the alkyl group or alkoxy group on the aromatic nucleus; a phenylmethyl group, a naphthylmethyl group, an aralkyl group substituted with the alkyl group or alkoxy group on the aromatic nucleus, or the like Is mentioned. Among them, heat resistance and moisture resistance in the cured product, since the active ester resin excellent in dielectric properties, it is preferred that R ² is a hydrogen atom.

  Z in the structural formulas (3-1) to (3-3) is a halogen atom or an alkyl ether structure moiety, specifically, a halogen atom such as a chlorine atom or a bromine atom; a methyl ether group, an ethyl ether group , Alkyl ether structure sites such as propyl ether group, isopropyl ether group, butyl ether group, t-butyl ether group and the like.

  The reaction of the phenol compound (a1) and the aromatic compound (a2) can be performed, for example, in the presence of an acid catalyst under a temperature condition of about 120 to 180 ° C.

  The reaction ratio between the phenol compound (a1) and the aromatic compound (a2) is such that the molar ratio [(a1) / (a2)] of the both is 3 / 0.1 to 1 / 0.5. It is preferable because the value of n in the structural formula (1) can be easily adjusted.

  Examples of the acid catalyst used in the reaction of the phenol compound (a1) and the aromatic compound (a2) include p-toluenesulfonic acid, dimethyl sulfate, diethyl sulfate, sulfuric acid, hydrochloric acid, and oxalic acid. These may be used alone or in combination of two or more. These catalysts are preferably used in an amount of 0.01 to 1% by mass with respect to the phenol compound (a1).

  In the present invention, among phenolic hydroxyl group-containing resins (A), those containing a bifunctional compound (α) having a value of n of 0 in the structural formula (1) in an area ratio of 40% or more in GPC measurement are used. It is preferable. In this case, after the reaction between the phenol compound (a1) and the aromatic compound (a2), the reaction product is dissolved in an organic solvent such as methyl isobutyl ketone, and the bifunctional compound (α) is extracted under alkaline conditions. The content of the bifunctional compound (α) can be increased by reprecipitation of the bifunctional compound (α) under acidic conditions or by reprecipitation by diluting in a large amount of water. Alternatively, the content of the functional substance (α) can be increased by an ultrafiltration membrane or the like.

  The aromatic dibasic acid or its halide (B) used in the present invention is, for example, isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid. Acids, naphthalene-2,7-dicarboxylic acids, acid fluorides, acid chlorides, acid bromides, acid iodides, and aromatic nuclei substituted with alkyl groups having 1 to 4 carbon atoms or alkoxy groups And the following structural formulas (b-1) to (b-6)

（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、Ｒ^４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Ｖ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、Ｗはヒドロキシル基又はハロゲン原子を表し、ｐ、ｑは１〜４の整数である。）
の何れかで表される化合物等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。中でも、硬化性に優れる活性エステル樹脂が得られることから、イソフタル酸のジクロライド又はテレフタル酸のジクロライドが好ましく、イソフタル酸のジクロライドがより好ましい。

(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 each R ⁴ 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 V 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, W represents a hydroxyl group or a halogen atom, and p and q are integers of 1 to 4.)
Or a compound represented by any of the above. These may be used alone or in combination of two or more. Among them, since an active ester resin having excellent curability is obtained, isophthalic acid dichloride or terephthalic acid dichloride is preferable, and isophthalic acid dichloride is more preferable.

  The aromatic monohydroxy compound (C) used in the present invention is, for example, an alkylphenol such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol; o-phenylphenol, p-phenylphenol, 2 -Aralkylphenols such as benzylphenol, 4-benzylphenol and 4- (α-cumyl) phenol; and naphthol compounds such as 1-naphthol and 2-naphthol. These may be used alone or in combination of two or more. Among them, 1-naphthol or 2-naphthol is preferable because a cured product having excellent heat resistance and moisture absorption resistance can be obtained.

  The reaction of the phenolic hydroxyl group-containing resin (A), the aromatic dibasic 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. These may be used alone or in combination of two or more. 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.

  The reaction is preferably carried out in an organic solvent because the reaction control becomes easy. 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. These may be used alone or as a mixed solvent of two or more.

  The reaction ratio of the phenolic hydroxyl group-containing resin (A), the aromatic dibasic acid or its halide (B), and the aromatic monohydroxy compound (C) can be appropriately changed according to the desired molecular design. In particular, since the active ester resin is more excellent in solvent solubility and has 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 dibasic acid or its halide (B). The phenolic hydroxyl group of the functional hydroxyl group-containing resin (A) is in the range of 0.25 to 2.00 mol, and the hydroxyl group of the aromatic monohydroxy compound (C) is 0.05 to 0.75 mol. It is preferable to use each raw material in the ratio which becomes a range.

  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 functional group equivalent of the active ester resin of the present invention is a cured product having excellent curability and low dielectric constant and low priority 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. Is preferably in the range of 200 to 360 g / equivalent, more preferably in the range of 220 to 350 g / equivalent, and still more preferably in the range of 220 to 240 g / equivalent.

  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 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, and 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 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 a high calculation 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. GPC was measured under the following conditions.

<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).

Example 1 Production of Active Ester Resin (1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 203.0 g of isophthalic acid chloride (2.0 moles of acid chloride group) 1-naphthol 57.6 g (0.4 mol) and 1094 g of toluene were charged, and the system was dissolved while substituting with nitrogen under reduced pressure. Subsequently, phenolic hydroxyl group-containing resin (A-1) having a molecular structure represented by the following structural formula (I) (Maywa Kasei Co., Ltd. “MEH-7851-SS” hydroxyl group equivalent 202 g / equivalent, area ratio in GPC measurement 50% of the content of bifunctional compound (α) whose value of n calculated from 0 is 0) 505.0 g (2.5 mol of phenolic hydroxyl group) is dissolved while the inside of the system is purged with nitrogen under reduced pressure. I let you. 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. After completion of the dropping, stirring was continued for 1.0 hour, and after completion of the reaction, the solution was allowed to stand for separation to remove the aqueous layer. 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, followed by standing and separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Toluene was distilled off by distillation to obtain an active ester resin (1).

（式中ｎは繰り返し単位数を表し、０又は１以上の整数である。）

(In the formula, n represents the number of repeating units and is 0 or an integer of 1 or more.)

Example 2 Production of Active Ester Resin (2) The following structural formula (II) is shown in a flask equipped with a cock for wastewater disposal at the bottom where a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer are attached. Phenolic hydroxyl group-containing resin (Maywa Kasei Co., Ltd. “MEH (C) -7800-4S” hydroxyl group equivalent 169 g / equivalent, n-value is 0) ) 300 g and methyl isobutyl ketone 600 g were charged and dissolved. Thereafter, 300 g of 3% aqueous sodium hydroxide solution was added 5 times in total to extract the bifunctional compound (α). After adjusting the pH to 2 by adding hydrochloric acid to the aqueous sodium hydroxide solution from which the bifunctional compound (α) was extracted, the precipitated bifunctional compound (α) was extracted again with methyl isobutyl ketone. Thereafter, methyl isobutyl ketone was distilled off by distillation to obtain 60 g of a phenolic hydroxyl group-containing resin (A-2) having a bifunctional (α) content calculated from the area ratio in GPC measurement of 80%. The obtained phenolic hydroxyl group-containing resin (A-2) had a hydroxyl group equivalent of 155 g / equivalent.

（式中ｎは繰り返し単位数を表し、０又は１以上の整数である。）

(In the formula, n represents the number of repeating units and is 0 or an integer of 1 or more.)

  Next, Example 1 is the same as Example 1 except that 505.0 g of the phenolic hydroxyl group-containing resin (A-1) used in Example 1 is changed to 387.5 g of the phenolic hydroxyl group-containing resin (A-2) obtained above. The same operation was performed to obtain an active ester resin (2).

Example 3 Production of Active Ester Resin (3) 300 g of the phenolic hydroxyl group-containing resin (“MEH (C) -7800-4S” manufactured by Meiwa Kasei Co., Ltd.) used in Example 2 was added to the phenolic hydroxyl group-containing resin (A-1). ) (Maywa Kasei Co., Ltd. “MEH-7851-SS” hydroxyl group equivalent 202 g / equivalent, n value calculated from area ratio in GPC measurement is 0, content 48% of bifunctional compound (α)) to 300 g Except for the change, the same operation as in Example 2 was performed to obtain 100 g of phenolic hydroxyl group-containing resin (A-3) having a 96% content of the bifunctional compound (α) calculated from the area ratio in GPC measurement. It was. The obtained phenolic hydroxyl group-containing resin (A-3) had a hydroxyl group equivalent of 187 g / eq.

  Next, Example 1 is used except that 505.0 g of the phenolic hydroxyl group-containing resin (A-1) used in Example 1 is changed to 467.5 g of the phenolic hydroxyl group-containing resin (A-3) obtained above. The same operation as was performed to obtain an active ester resin (3).

Comparative Example 1 Production of Active Ester Resin (1 ′) 203.0 g of isophthalic acid chloride (2.0 mol of acid chloride group) in a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer And 1800 g of toluene were charged, and the system was dissolved while substituting with nitrogen under reduced pressure. Next, 57.6 g (0.4 mol) of 1-naphthol and a dicyclopentadiene-modified phenol resin having a molecular structure represented by the following structural formula (III) (hydroxyl equivalent: 165 g / eq, calculated from an area ratio in GPC measurement) 412.5 g (2.5 mol of phenolic hydroxyl group) of the bifunctional compound (α) whose n value is 0 is prepared, and the inside of the system is dissolved under reduced pressure nitrogen. 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. After completion of the dropping, stirring was continued for 1.0 hour, and after completion of the reaction, the solution was allowed to stand for separation to remove the aqueous layer. 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, followed by standing and separation to remove the aqueous layer. This operation was repeated until the pH of the water tank reached 7. Toluene was distilled off by distillation to obtain an active ester resin (1 ′).

（式中ｌは０又は１である。ｎは繰り返し単位数を表し、０又は１以上の整数である。）

(In the formula, l is 0 or 1. n represents the number of repeating units and is 0 or an integer of 1 or more.)

<Solvent solubility test>
The active ester resin obtained above was dissolved in methyl ethyl ketone, and methyl ethyl ketone was added until turbidity occurred. The nonvolatile fraction at the time when turbidity occurred was measured. The results are shown in Table 1. It shows that it is excellent in solvent solubility, so that a value is small.

Examples 4 to 6 and Comparative Example 2
An epoxy resin composition was prepared in the following manner, a laminate was prepared, and various evaluation tests were performed. The results are shown in Table 2.

<Preparation of epoxy resin composition>
For 100 g of epoxy resin (“HP-7200H” dicyclopentadiene phenol type epoxy resin manufactured by DIC, melt viscosity 0.30 poise at 150 ° C., epoxy group equivalent 277 g / equivalent), the number of functional groups in the active ester resin is epoxy group. Both are blended so as to be equal to the number of moles, dimethylaminopyridine is added in an amount of 0.5% by mass based on the total mass of the epoxy resin and the active ester resin, and the non-volatile content is adjusted to 58% by mass with methyl ethyl ketone. An epoxy resin composition was obtained.

<Creation of laminated board>
A laminate was prepared under the following 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

<Glass transition temperature>
The laminated plate obtained above was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece. The temperature at which the elastic modulus change is maximum (the tan δ change rate is the largest) was evaluated as the glass transition temperature using a heating rate of 3 ° C./min.

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

<Hygroscopic resistance>
The laminate obtained above was cut into a size of 25 mm in width and 75 mm in length, and this was used as a test piece and allowed to stand for 168 hours in an atmosphere of 85 ° C./85% RH, and the change in weight before and after the treatment was measured.

<Thermal conductivity>
Using a thermal conductivity meter “QTM-500” manufactured by Kyoto Electronics Co., Ltd., it was measured by the unsteady hot wire method.

Claims (10)

The following structural formula (1)

[Wherein 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, an aryl group or an aralkyl group, and m is an integer of 1 to 3 It is. X is each independently the following structural formulas (X-1) to (X-3)

(Wherein R ² is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l is an integer of 1 to 3) Y is any one of an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, and a sulfone group.
It is a structural part represented by either. n represents the number of repeating units and is 0 or an integer of 1 or more. ]
A phenolic hydroxyl group-containing resin (A), an aromatic dibasic acid or its halide (B), and an aromatic monohydroxy compound (C) represented by
The phenolic hydroxyl group contained in the phenolic hydroxyl group-containing resin (A) is 0.25 to 2.00 mol per 1 mol in total of the carboxyl group or acid halide group contained in the aromatic dibasic acid or its halide (B). It becomes the range and the hydroxyl groups of the aromatic monohydroxy compound (C) has the features and Turkey obtained by reacting with the raw material at a rate in the range of 0.05 to 0.75 moles Active ester resin. 2. The phenolic hydroxyl group-containing resin (A) contains a bifunctional compound (α) having a value of n of 0 in the structural formula (1) in an area ratio of 40% or more in GPC measurement. Active ester resin. 2. The phenolic hydroxyl group-containing resin (A) contains a bifunctional compound (α) having a value of n of 0 in the structural formula (1) in an area ratio of 70% or more in GPC measurement. Active ester resin. The active ester resin according to any one of claims 1 to 3 , wherein X in the structural formula (1) is a structural moiety represented by the structural formula (X-1) or (X-2). The active ester resin according to any one of claims 1 to 4, wherein the aromatic monohydroxy compound (C) is 1-naphthol or 2-naphthol. 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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