JP2014065753A - Active ester resin, curable resin composition, cured product thereof, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin cured product that is superior in heat-resistance, is small in a change of heat-resistance after thermal hysteresis, and is low in a dielectric constant and dielectric loss tangent, and provide an active ester resin curing agent that provides the cured product.SOLUTION: This invention provides: an active ester resin curing agent that is a reactant of polycondensate (a) of α-naphthol compound, β-naphthol compound, and formaldehyde, and monocarboxylic acid compound or its halide (b), wherein the percentage of content of trimer is 15-35% and the percentage of content of dimer is 1-25% (both are area ratios based on GPC measurements), and at least one phenolic hydroxyl group included in the trimer and/or dimer is substituted by an ester forming structural moiety selected from the group consisting of benzoyl group, benzoyl group ring-substituted by 1-4C alkyl group, naphthoyl group, naphthoyl group ring-substituted by 1-4C alkyl group, and 2-6C acyl group; and an epoxy resin containing the curing agent.

Description

  The present invention provides an active ester resin in which the resulting cured product has excellent heat resistance, a small change in heat resistance after heat history, and a low dielectric constant and dielectric loss tangent, and a curable resin composition containing the same, The present invention relates to a cured product, a semiconductor sealing material, a prepreg, a circuit board, and a buildup film.

A curable resin composition containing an epoxy resin and a curing agent as an essential component exhibits excellent heat resistance and insulation in the cured product, and is therefore widely used in electronic component applications such as semiconductors and multilayer printed boards. Yes. Among these electronic component applications, in the technical field of multilayer printed circuit board insulating materials, in recent years, signal speed and frequency have been increasing in various electronic devices. However, with the increase in signal speed and frequency, it is becoming difficult to obtain a low dielectric loss tangent while maintaining a sufficiently low dielectric constant.

  Therefore, it is desired to provide a curable resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even with respect to high-speed and high-frequency signals. It is rare. As a material capable of realizing these low dielectric constants and low dielectric loss tangents, a technique using an active ester compound obtained by esterifying a phenolic hydroxyl group in a phenol novolac resin as a curing agent for an epoxy resin is known (see below, Patent Document 1).

  However, because of the trend toward higher frequency and smaller size in electronic components, multilayer printed circuit board insulating materials are required to have extremely high heat resistance, and active esters obtained by esterifying phenolic hydroxyl groups in the above-described phenol novolac resins. The compound had a reduced crosslink density of the cured product due to the introduction of the ester structure, and the cured product did not have sufficient heat resistance, and the heat resistance change after heat history was large. Further, its low dielectric constant and low dielectric loss tangent did not satisfy the ever-increasing level of market demand.

JP 7-82348 A

  Accordingly, the problem to be solved by the present invention is that the cured product obtained has an excellent heat resistance, a small change in heat resistance after heat history, and an active ester resin having a low dielectric constant and dielectric loss tangent. It is in providing the curable resin composition to contain, its hardened | cured material, semiconductor sealing material, a prepreg, a circuit board, and a buildup film.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are a reaction product of a naphthol novolak resin and a monocarboxylic acid compound or a halide (b) thereof, and a trimer and a dimer having a specific structure. The active ester resin containing the body at a predetermined ratio shows high heat resistance because of its high reactivity, the heat resistance change after heat history is small, and the dielectric constant and dielectric loss tangent. And the present invention has been completed.

That is, the present invention is a reaction product of an α-naphthol compound, a β-naphthol compound, and a polycondensate of formaldehyde (a) with a monocarboxylic acid compound or a halide (b) thereof,
The following structural formula (1)

［式中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を示し、Ｚはベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）である。］
で表される３量体（ｘ１）と、
下記構造式（２）

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z represents a benzoyl group or 1 to 4 carbon atoms. Benzoyl group, naphthoyl group, and naphthoyl group nucleus-substituted with 1 to 3 of alkyl groups having 1 to 4 carbon atoms, acyl having 2 to 6 carbon atoms An ester-forming structural site (z1) selected from the group consisting of groups, or a hydrogen atom (z2). ]
A trimer (x1) represented by:
The following structural formula (2)

［式中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を示し、Ｚはベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）である。］
で表される２量体（ｘ２）とを含有しており、前記３量体（ｘ１）の含有率がＧＰＣ測定における面積比率で１５〜３５％の範囲となる割合であり、前記２量体（ｘ２）の含有率がＧＰＣ測定における面積比率で１〜２５％の範囲となる割合であり、かつ、前記３量体（ｘ１）と前記２量体（ｘ２）とが有するＸのうち少なくとも一つが前記エステル形成構造部位（ｚ１）であることを特徴とする活性エステル樹脂に関する。

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z represents a benzoyl group or 1 to 4 carbon atoms. Benzoyl group, naphthoyl group, and naphthoyl group nucleus-substituted with 1 to 3 of alkyl groups having 1 to 4 carbon atoms, and 2 to 6 carbon atoms. An ester-forming structural site (z1) selected from the group consisting of acyl groups, or a hydrogen atom (z2). ]
A dimer (x2) represented by the formula, wherein the content of the trimer (x1) is a ratio of 15 to 35% in terms of area ratio in GPC measurement, and the dimer The content ratio of (x2) is a ratio that is in the range of 1 to 25% in the area ratio in GPC measurement, and at least one of X included in the trimer (x1) and the dimer (x2) The present invention relates to an active ester resin characterized in that one is the ester-forming structural site (z1).

  The present invention further relates to a curable resin composition comprising the above-mentioned active ester resin and epoxy resin as essential components.

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

  The present invention further relates to a semiconductor sealing material comprising a curable resin composition containing, in addition to the active ester resin and the epoxy resin, an inorganic filler in a proportion of 70 to 95% by mass in the composition.

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with a solution obtained by diluting the curable 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 curable 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 material obtained by diluting the curable resin composition in an organic solvent onto a base film and drying it.

  According to the present invention, the resulting cured product is excellent in heat resistance, has little change in heat resistance after heat history, and has a low dielectric constant and dielectric loss tangent, and an active ester resin containing the active ester resin. Product, its cured product, semiconductor encapsulating material, prepreg, circuit board and build-up film can be provided.

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

Hereinafter, the present invention will be described in detail.
The active ester resin of the present invention is a reaction product of a polycondensate (a) of an α-naphthol compound, a β-naphthol compound, and formaldehyde with a monocarboxylic acid compound or a halide (b) thereof.
The following structural formula (1)

［式中、Ｒ^１及びＲ^２はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を示し、Ｚはベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）である。］
で表される３量体（ｘ１）と、
下記構造式（２）

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z represents a benzoyl group or 1 to 4 carbon atoms. Benzoyl group, naphthoyl group, and naphthoyl group nucleus-substituted with 1 to 3 of alkyl groups having 1 to 4 carbon atoms, acyl having 2 to 6 carbon atoms An ester-forming structural site (z1) selected from the group consisting of groups, or a hydrogen atom (z2). ]
A trimer (x1) represented by:
The following structural formula (2)

［式中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を示し、Ｚはベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）である。］
で表される２量体（ｘ２）とを含有しており、前記３量体（ｘ１）の含有率がＧＰＣ測定における面積比率で１５〜３５％の範囲となる割合であり、前記２量体（ｘ２）の含有率がＧＰＣ測定における面積比率で１〜２５％の範囲となる割合であり、かつ、前記３量体（ｘ１）と前記２量体（ｘ２）とが有するＸのうち少なくとも一つが前記エステル形成構造部位（ｚ１）であることを特徴としている。

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z represents a benzoyl group or 1 to 4 carbon atoms. Benzoyl group, naphthoyl group, and naphthoyl group nucleus-substituted with 1 to 3 of alkyl groups having 1 to 4 carbon atoms, and 2 to 6 carbon atoms. An ester-forming structural site (z1) selected from the group consisting of acyl groups, or a hydrogen atom (z2). ]
A dimer (x2) represented by the formula, wherein the content of the trimer (x1) is a ratio of 15 to 35% in terms of area ratio in GPC measurement, and the dimer The content ratio of (x2) is a ratio that is in the range of 1 to 25% in the area ratio in GPC measurement, and at least one of X included in the trimer (x1) and the dimer (x2) One of them is the ester forming structure site (z1).

  That is, the active ester resin of the present invention is a reaction product of a polycondensate (a) using α-naphthol compound, β-naphthol compound, and formaldehyde as raw materials and a monocarboxylic acid compound or a halide (b) thereof. In addition, a mixture containing various resin structures includes a predetermined amount of the trimer (x1) and the dimer (x2). The trimer (x1), which is an essential component of the active ester resin of the present invention, has high molecular orientation and suppresses molecular motion in the cured product, so that the dielectric constant and dielectric loss tangent can be kept low. . Further, since the trimer (x1) has high reactivity and the cured product is closely cross-linked, it has excellent heat resistance and a small change in heat resistance after heat history.

  Here, as described above, the content of the trimer (x1) is in the range of 15 to 35% in terms of the area ratio in the GPC measurement, and when it exceeds 35% by mass, the solvent solubility of the epoxy resin decreases. . On the other hand, when it is less than 15%, the heat resistance change after the thermal history of the cured product becomes large.

  Specifically, such trimer (x1) has the following structural formulas (1-1) to (1-6).

で表される化合物が挙げられる。これらのなかでも特に前記構造式１−１で表されるもの、即ち、前記構造式（１）におけるＲ^１及びＲ^２が、全て水素原子であるものが、硬化物における熱履歴後の耐熱性変化が小さくなる点から好ましい。

The compound represented by these is mentioned. Among these, particularly those represented by the structural formula 1-1, that is, those in which R ¹ and R ² in the structural formula (1) are all hydrogen atoms, the heat resistance after the heat history in the cured product. This is preferable from the viewpoint of small change.

  In this invention, the heat resistance change after the heat history of hardened | cured material can be made small by including the said dimer (x2) 1% or more. Moreover, since the compounding quantity of this dimer (x2) is 25% or less, the outstanding solvent solubility can be expressed and the utilization as a varnish for printed wiring boards is attained.

  Specifically, such a dimer (x2) has the following structural formulas (2-1) to (2-6).

で表される化合物が挙げられる。これらのなかでも特に前記構造式２−１で表されるもの、即ち、前記構造式（２）におけるＲ^１及びＲ^２が、全て水素原子であるものが、硬化物における熱履歴後の耐熱性変化が小さくなる点から好ましい。

The compound represented by these is mentioned. Among these, particularly those represented by the structural formula 2-1, that is, those in which R ¹ and R ² in the structural formula (2) are all hydrogen atoms, the heat resistance after the heat history in the cured product. This is preferable from the viewpoint of small change.

  Z in the trimer (x1) and the dimer (x2) is, as described above, a benzoyl group, a benzoyl group that is substituted with one to three alkyl groups having 1 to 4 carbon atoms, or naphthoyl. An ester-forming structural site (z1) selected from the group consisting of a group and a naphthoyl group nucleus-substituted with 1 to 3 of an alkyl group having 1 to 4 carbon atoms, an acyl group having 2 to 6 carbon atoms, or , A hydrogen atom (z2), and at least one of Z included in the trimer (x1) and the dimer (x2) is the ester-forming structural site (z1). At this time, the abundance ratio of the ester-forming structural site (z1) and the hydrogen atom (z2) is the total of the ester-forming structural site (z1) and the hydrogen atom (z2). It is preferable that z1) is a ratio of 40% or more from the viewpoint of excellent dielectric properties of the cured product, and the ratio of the ester-forming structure part (z1) to 65% or more with respect to the total of both is more preferable. preferable.

  Thus, all of X in the trimer (x1) or the dimer (x2) may be the ester-forming structure site (x1), but a part of X is a hydrogen atom ( x2), that is, by having a part of the phenolic hydroxyl group, the curability is good and the effect of improving the heat resistance becomes remarkable.

  Here, the benzoyl group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms represented by Z is 2,4-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 2,4,4, 6-trimethylbenzoyl group, 2-ethylbenzoyl group, 4-ethylbenzoyl group 2-t-butyl-4-ethylbenzoyl group, 4-i-propylbenzoyl group, 4-t-butylbenzoyl group, 2,6-di -T-butylbenzoyl group is mentioned.

  In addition, a naphthoyl group that is nucleus-substituted with one or two alkyl groups having 1 to 4 carbon atoms includes a 2-methyl-1-naphthol group, a 4-methyl-1-naphthoyl group, and 2-ethyl-1- Naphthoyl group, 3-methyl-4-ethyl-2-naphthoyl group, 2-propyl-1-naphthoyl group, 2-propyl-4-ethyl-1-naphthoyl group, 6-propyl-2-naphthoyl group, 2-t -Butyl-1-naphthyl group, 3-t-butyl-1-naphthyl group, 4-t-butyl-1-naphthyl group and the like can be mentioned. Examples of the acyl group having 2 to 6 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and caproyl group.

  Among the above-mentioned structures, the ester-forming structure site (z1) is an acetyl group or a benzoyl group, particularly from the viewpoint of excellent dielectric properties at the time of curing, particularly a good reactivity with the epoxy resin described later. Or a naphthoyl group is preferable, and a benzoyl group is particularly preferable.

  In addition to the trimer (x1) and the dimer (x2), the active ester resin of the present invention further includes the following structural formula (3).

［式中、Ｚはベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）であり、Ｒ^１及びＲ^２はそれぞれ独立して水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を示し、ｎは繰り返し単位であって２〜１０の整数である。］
で表されるカリックスアレーン化合物（ｘ３）を含有しても良い。

[Wherein Z is a benzoyl group, a benzoyl group nucleosubstituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, a naphthoyl group, or 1 to 3 alkyl groups with 1 to 4 carbon atoms. A nucleus-substituted naphthoyl group, an ester-forming structural site (z1) selected from the group consisting of an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2), wherein R ¹ and R ² are each independently A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms are shown, and n is a repeating unit and is an integer of 2 to 10. ]
The calixarene compound (x3) represented by these may be contained.

  In this case, the content of each component in the active ester resin is such that the content of the trimer (x1) is in the range of 15 to 35% in terms of the area ratio in GPC measurement, and the dimer (x2 ) Is a ratio in which the area ratio in GPC measurement is in the range of 1 to 25%, and the content ratio of the calixarene compound (x3) is in the ratio in which the area ratio in GPC measurement is in the range of 1 to 40%. Preferably there is.

The content of the trimer (x1), the dimer (x2), and the calixarene compound (x3) in the active ester in the present invention is calculated by GPC measurement under the following conditions. The ratio of the peak area of each structure to the total peak area of the epoxy resin.
<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 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).

  Moreover, Z of the calixarene compound (x3) is 1 to 3 of a benzoyl group and an alkyl group having 1 to 4 carbon atoms, like Z in the trimer (x1) and the dimer (x2). Selected from the group consisting of a benzoyl group nucleosubstituted with naphthoyl, a naphthoyl group nuclei substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, and an acyl group with 2 to 6 carbon atoms Ester-forming structural site (z1) or hydrogen atom (z2), and at least one of X of the trimer (x1), the dimer (x2), or the calixarene compound (x3) Is the ester-forming structural site (z1). At this time, the abundance ratio of the ester-forming structural site (z1) and the hydrogen atom (z2) is the total of the ester-forming structural site (z1) and the hydrogen atom (z2). It is preferable that z1) is a ratio of 40% or more from the viewpoint of excellent dielectric properties of the cured product, and the ratio of the ester-forming structure part (z1) to 65% or more with respect to the total of both is more preferable. preferable.

R ¹ and R ² in the structural formula (3) are synonymous with those in the structural formula (1), and the heat resistance change after the thermal history in the cured product is small, so both are hydrogen atoms. It is preferable. The repeating unit n is an integer of 2 to 10, but has a more rigid and stable structure, and the balance between the dielectric properties of the cured product and the heat resistance change after the thermal history of the cured product is further improved. Therefore, n is preferably 4.

  The active ester resin of the present invention may contain a high molecular weight component (x4) in addition to the trimer (x1), the dimer (x2), and the calixarene compound (x3) described above.

  Such a high molecular weight component (x4) is a high molecular weight component excluding the above (x1) to (x3) in the active ester resin of the present invention, and specifically, the following structural formula (I)

［式中、Ｚはベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）であり、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を表す。］
で表される構造ユニット（Ｉ）と、
下記、構造式（ＩＩ）

[Wherein Z is a benzoyl group, a benzoyl group nucleosubstituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, a naphthoyl group, or 1 to 3 alkyl groups with 1 to 4 carbon atoms. A nucleus-substituted naphthoyl group, an ester-forming structural site (z1) selected from the group consisting of an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2), wherein R ¹ and R ² are each independently A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. ]
A structural unit (I) represented by:
Structural formula (II) below

［式中、Ｚはベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）であり、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基を示し、ｍは繰り返し単位であり０以上の整数である。］
で表される構造ユニット（ＩＩ）とが、メチレン結合により結節され、高分子量化した基本構造を有する活性エステル樹脂である。

[Wherein Z is a benzoyl group, a benzoyl group nucleosubstituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, a naphthoyl group, or 1 to 3 alkyl groups with 1 to 4 carbon atoms. A nucleus-substituted naphthoyl group, an ester-forming structural site (z1) selected from the group consisting of an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2), wherein R ¹ and R ² are each independently A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, m is a repeating unit and is an integer of 0 or more. ]
Is an active ester resin having a basic structure which is knotted by a methylene bond and has a high molecular weight.

  The dimer (x2), the trimer (x1), and the calixarene compound (x3) are detected in this order from the longest retention time by GPC measurement, and the high molecular weight component (x4) is the calixarene compound (x3). Therefore, it is a component detected in a region having a short holding time. The proportion of the high molecular weight component (x4) in the active ester resin is preferably an area ratio in the GPC measurement in the range of 40 to 75% by mass because the solvent solubility of the active ester resin is excellent. The specific structure of the high molecular weight component (x4) includes a resin structure (x4-1) in which the structural unit (I) and the structural unit (II) are alternately bonded via a methylene bond, and the structure. The resin structure (x4-2) in which the structural unit (I) is bonded to both ends of the unit (II) through a methylene bond is exemplified. In the present invention, the resin structure (x4-2) is used from the viewpoint of low thermal expansion. What has is preferable. In the resin structure (x4-2), the structural unit (I) is located at both ends of the structure as described above, but is bonded to a methylene bond among the two bonds of the structural unit (I). A hydrogen atom is bonded to a non-bonded hand.

  In addition to the α-naphthol compound, β-naphthol compound, and formaldehyde as a raw material component of the polycondensate (a), when the other novolak resin is used in combination, the high molecular weight component (x4) is: The structural unit (I), the structural unit (II), and the other novolak resin are knotted to each other through a methylene bond to have a high molecular weight. In addition, when using the said other novolak resin together as a raw material component of the said polycondensate at the time of manufacture, the usage-amount is 5 per 100 mass parts of total mass of (alpha) -naphthol compound and (beta) -naphthol compound used as a raw material. It is preferable that it is 30 mass parts from the point which is excellent in the reactivity of the active ester resin finally obtained.

  The active ester resin of the present invention is such that the functional group equivalent based on the total number of functional groups of the carbonyloxy group and phenolic hydroxyl group in the active ester resin is in the range of 200 to 300 g / eq. From the point that the balance between the property and the dielectric property is good.

The active ester resin of the present invention described in detail above can be produced, for example, by the following method 1 or method 2.
Method 1: A β-naphthol compound and formaldehyde are reacted in the presence of an organic solvent and an alkali catalyst, and then the α-naphthol compound is added and reacted in the presence of formaldehyde to obtain a polycondensate (a) (step) 1) Next, the obtained polycondensate (a) is reacted with a monocarboxylic acid compound or a halide (b) thereof (step 2) to obtain a target active ester resin.
Method 2: α-naphthol compound, β-naphthol compound, and formaldehyde are reacted in the presence of an organic solvent and an alkali catalyst to obtain a polycondensate (a) (step 1), and then the resulting polycondensate ( A method of obtaining a target active ester resin by reacting a) with a monocarboxylic acid compound or a halide (b) thereof (step 2).

  In the present invention, the trimer (x1) and the 2 are obtained by using an alkali catalyst as a reaction catalyst in Step 1 of the method 1 or 2 and using an organic solvent in a small amount with respect to the raw material components. The abundance ratio of the monomer (x2) and the calixarene compound (x3) in the active ester resin can be adjusted to a predetermined range, and the abundance ratio of the high molecular weight component (x4) is also in an appropriate range.

  Examples of the alkali catalyst used herein include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, inorganic alkalis such as metal sodium, metal lithium, sodium hydride, sodium carbonate, and potassium carbonate. The amount used is 0.01 to 2.0 times the amount of the raw material components α-naphthol compound, β-naphthol compound, and, if necessary, the total number of phenolic hydroxyl groups of the other novolak resin on a molar basis. It is preferable that it is the range.

  Examples of the organic solvent include methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. Among these, isopropyl alcohol is particularly preferred from the viewpoint of relatively high molecular weight of the polycondensate (a). In the present invention, the amount of the organic solvent used is that of the raw material components α-naphthol compound and β-naphthol compound, and when the other novolak resin is used in combination, the raw material α-naphthol compound and β-naphthol compound are used. Presence of the trimer (x1), the dimer (x2), and the calixarene compound (x3) in the active ester resin to be in the range of 5 to 70 parts by mass per 100 parts by mass of the total mass This is preferable because the ratio can be easily adjusted to a predetermined range.

  Specifically, the α-naphthol compound which is a raw material component includes α-naphthol and an alkyl group such as a methyl group, an ethyl group, a propyl group and a t-butyl group, and an alkoxy group such as a methoxy group and an ethoxy group. In addition, the β-naphthol compound includes β-naphthol and alkyl groups such as a methyl group, an ethyl group, a propyl group, and a t-butyl group, and an alkoxy group such as a methoxy group and an ethoxy group. Examples include compounds substituted by nuclei. Among these, α-naphthol and β-naphthol having no substituent are preferable from the viewpoint that the heat resistance change after heat history in the cured product of the finally obtained active ester resin is reduced.

  On the other hand, the formaldehyde used here may be a formalin solution in an aqueous solution state or paraformaldehyde in a solid state.

  The ratio of α-naphthol compound and β-naphthol compound used in Step 1 of Method 1 or Method 2 is such that the molar ratio (α-naphthol compound / β-naphthol compound) is [1 / 0.4] to [1. /1.2] It is preferable that the ratio of each component in the finally obtained active ester resin is easily adjusted.

  The reaction charge ratio of formaldehyde is a ratio of 0.6 to 2.0 times the amount of formaldehyde on a molar basis with respect to the total number of moles of α-naphthol compound and β-naphthol compound. From the point which is excellent in it, it is preferable that it is the ratio used as 0.6-1.5 times amount.

  In the present invention, as described above, in addition to the α-naphthol compound, β-naphthol compound, and formaldehyde as raw material components, another novolak resin can be used in combination. Here, as other novolak resins to be used, for example, phenol novolak resins and cresol novolak resins can be mentioned, and by partially using these in combination, the solvent solubility of the active ester resin finally obtained is drastically improved. be able to. These phenol novolak resins and cresol novolak resins are those having a softening point of 60 to 120 ° C. from the viewpoint that the solvent solubility can be improved without degrading the performance such as heat resistance and heat resistance change with respect to thermal history in the present invention. It is preferable.

  When the other novolak resin is used as a part of the raw material, the reaction charge ratio of each raw material component in Step 1 of Method 1 or Method 2 is a molar ratio (α-naphthol compound and β-naphthol compound / other novolaks). It is easy to adjust the ratio of each component in the active ester resin finally obtained when the number of aromatic nuclei in the resin is in the range of [1 / 0.06] to [1 / 0.36]. Further, the amount of formaldehyde used is 0.6 to 2 on a molar basis with respect to the total number of moles of aromatic nuclei, α-naphthol compounds and β-naphthol compounds in other novolak resins. It is preferable that it is a ratio which becomes a ratio which becomes 0.6 times 1.5 times from the point which is the ratio used as 0.0 time amount, and is especially excellent in the balance of heat resistance and solvent solubility.

  In Step 1 of Method 1, a reaction vessel is charged with a predetermined amount of β-naphthol compound, formaldehyde, an organic solvent, and an alkali catalyst and reacted at 40 to 100 ° C. After the reaction is completed, an α-naphthol compound (required) Depending on the case, formaldehyde) can be further added and reacted under the temperature condition of 40 to 100 ° C. to obtain the desired polycondensate. In this case, when another novolak resin is used in combination, it is preferably added to the reaction vessel together with the α-naphthol compound.

  After completion of the reaction in Step 1, neutralization or water washing is performed until the pH value of the reaction mixture becomes 4 to 7 after the reaction is completed. The neutralization treatment and the water washing treatment may be performed according to conventional methods. For example, acidic substances such as acetic acid, phosphoric acid, and sodium phosphate can be used as the neutralizing agent. After neutralization or water washing treatment, the organic solvent is distilled off under reduced pressure heating to obtain the desired polycondensate.

  In step 1 of Method 2, when a predetermined amount of β-naphthol compound, α-naphthol compound, formaldehyde, an organic solvent, an alkali catalyst, and other novolak resins are used in combination in the reaction vessel, the novolak resin is charged. The desired polycondensate can be obtained by reacting at 40 to 100 ° C. In this case, when another novolak resin is used in combination, it is preferably added to the reaction vessel together with the α-naphthol compound.

  After completion of the reaction in Step 1, neutralization or water washing is performed until the pH value of the reaction mixture becomes 4 to 7 after the reaction is completed. The neutralization treatment and the water washing treatment may be performed according to conventional methods. For example, acidic substances such as acetic acid, phosphoric acid, and sodium phosphate can be used as the neutralizing agent. After neutralization or water washing treatment, the organic solvent is distilled off under reduced pressure heating to obtain the desired polycondensate.

  Next, in Step 2 of Method 1 or Method 2, the target active ester resin is obtained by reacting the polycondensate (a) obtained in Step 1 with a monocarboxylic acid compound or a halide (b) thereof. It is a manufacturing process.

  The monocarboxylic acid compound used in Step 2 or its halide (b) is specifically a phenyl group, a naphthyl group substituted with 1 to 3 of a phenyl group, a naphthyl group, or an alkyl group having 1 to 4 carbon atoms. Group, an aromatic monocarboxylic acid having a hydrocarbon structure selected from the group consisting of naphthyl groups substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, or a halide (b-1) ( Hereinafter, this is abbreviated as “aromatic monocarboxylic acid or its halide (b-1)”), or a saturated fatty acid having 2 to 5 carbon atoms or its halide (b-2) (hereinafter referred to as “ Abbreviated as “saturated fatty acid or its halide (b-2)”).

  Specifically, the aromatic monocarboxylic acid or its halide (b-1) is benzoic acid, methylbenzoic acid, 2,4-dimethylbenzoic acid, 2,6-dimethylbenzoic acid, 2,4,4, Alkylbenzoic acids such as 6-trimethylbenzoic acid, 2-ethylbenzoic acid, 4-ethylbenzoic acid, 2-t-butyl-4-ethylbenzoic acid, 4-i-propylbenzoic acid, 4-t-butylbenzoic acid 1-naphthoic acid, 2-naphthoic acid, 2-methyl-1-naphthoic acid, 4-methyl-1-naphthoic acid, 2-ethyl-1-naphthoic acid, 3-methyl-4-ethyl-2-naphthoic acid 2-propyl-1-naphthoic acid, 2-propyl-4-ethyl-1-naphthoic acid, 6-propyl-2-naphthoic acid, 2-t-butyl-1-naphthoic acid, 3-t-butyl-1 -Naphthoic acid, 4-t-butyl 1-naphthoic acid, as well as their acid fluorides, acid chlorides, acid bromides, acid halides such as acid iodide and the like.

  Further, the saturated fatty acid or its halide (b-2) specifically includes ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, and their acid fluorides, acid chlorides, acid bromides, And acid halides such as acid iodide.

  Among these, acid chlorides of benzoic acid and ethanoic acid are particularly preferable from the viewpoint of excellent dielectric properties.

  Specific examples of the reaction between the polycondensate (a) in Step 2 and the monocarboxylic acid compound or halide (b) thereof include a method of reacting them under a basic catalyst.

  The reaction ratio between the polycondensate (a) and the monocarboxylic acid compound or its halide (b) is such that the phenolic hydroxyl group in the polycondensate (a) and the monocarboxylic acid compound or its halide (b) Equivalent ratio with the carboxyl group or acid halide group [OH in (a) / carboxyl group or acid halide group in (b)] is a ratio of 1.0 / 0.40 to 1.0 / 1.0. It is preferable from the point that the solvent solubility of the obtained active ester resin is good.

  Examples of the alkali catalyst that can be used in the reaction of Step 2 include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.

  In the reaction of Step 2, each raw material component is preferably dissolved in an organic solvent and used for the reaction. Examples of the organic solvent used here include toluene and dichloromethane.

  After carrying out the reaction under the above conditions, an appropriate amount of water is added to the reaction solution to dissolve the produced salt. Thereafter, washing with water is repeated to remove the generated salt in the system, and further purification is performed by dehydration or filtration, and the organic solvent is removed by distillation to obtain the desired active ester resin.

  Next, the curable resin composition of the present invention comprises the active ester resin and the epoxy resin detailed above as essential components.

  The epoxy resin used here is bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, 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 co-condensed novolak type epoxy resin, naphthol-cresol co Denatured novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak type epoxy resin Resins. Among these epoxy resins, it is preferable to use a tetramethyl biphenol type epoxy resin, a biphenyl aralkyl type epoxy resin, or a novolac type epoxy resin from the viewpoint that a cured product having excellent flame retardancy can be obtained.

  The compounding amount of the active ester resin and the epoxy resin in the curable resin composition of the present invention is that the carbonyloxy group and the phenolic property in the active ester resin are excellent in terms of curability and various physical properties of the cured product. It is preferable that the ratio of the epoxy group in the epoxy resin is 0.8 to 1.2 equivalents with respect to 1 equivalent in total with the hydroxyl group.

In addition to the above-mentioned active ester resin and epoxy resin, the curable resin composition of the present invention may be used in combination with another curing agent for epoxy resin. As the curing agent for epoxy resin that can be used here, for example, curing agents such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like can be used. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives. Examples of the amide compound include dicyandiamide, Examples include polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. , Methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol -Cresol-condensed novolak resin, biphenyl-modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified Examples thereof include polyhydric phenol compounds such as phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine or benzoguanamine).

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are preferable from the viewpoint of flame retardancy, and specifically, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, phenol aralkyls. Resins, naphthol aralkyl resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins are preferred because of their excellent flame retardancy. .

  When the above-described curing agent for epoxy resin is used in combination, the amount used is sufficient to exhibit the excellent effects of the low dielectric constant and low dielectric loss tangent exhibited by the present invention. Therefore, the total curing agent including the active ester resin It is preferable that it is the range of 10-50 mass% in a component.

  Moreover, a hardening accelerator can also be suitably used together with the curable resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  Since the curable resin composition of the present invention described in detail above is excellent in solvent solubility, it can be diluted with an organic solvent and used. Examples of the organic solvent that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The amount used can be appropriately selected depending on the application. For example, in printed wiring board applications, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, dimethylformamide, and the non-volatile content of 40 to 80% by mass. It is preferable to use in the ratio which becomes. On the other hand, in build-up adhesive film applications, as organic solvents, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, It is preferable to use carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, and the nonvolatile content is 30 to 60% by mass. It is preferable to use in proportions.

  The thermosetting resin composition is a non-halogen flame retardant that substantially does not contain a halogen atom in order to exert flame retardancy, for example, in the field of printed wiring boards, as long as the reliability is not lowered. May be blended.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system 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.

  Examples of the organic phosphorus compound 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-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus 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.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of curable resin composition containing all of halogen-based flame retardant and other fillers and additives, 0.1 to 2.0 parts by mass of red phosphorus is used as a non-halogen flame retardant. It is preferable to mix in the range, and when using an organophosphorus compound, it is preferably mixed in the range of 0.1 to 10.0 parts by mass, particularly in the range of 0.5 to 6.0 parts by mass. It is preferable to do.

  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, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected according to the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in the range of 1-5 mass parts.

  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.

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. 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.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific 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.

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

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

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O 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. The glassy compound can be mentioned.

  The amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in 5-15 mass parts.

  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 or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of the curable resin composition in which all of epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives are blended, it is preferably blended in the range of 0.005 to 10 parts by mass. .

  An inorganic filler can be mix | blended with the curable resin composition of this invention 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 curable 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.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be obtained by uniformly mixing the above-described components. The curable resin composition of the present invention in which the epoxy resin of the present invention, a curing agent, and further, if necessary, a curing accelerator are blended can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Examples of uses in which the curable resin composition of the present invention is used include hard printed wiring board materials, flexible wiring board resin compositions, insulating materials for circuit boards such as build-up board interlayer insulating materials, semiconductor sealing materials, Examples include conductive pastes, build-up adhesive films, resin casting materials, and adhesives. Among these various applications, in hard printed wiring board materials, insulating materials for electronic circuit boards, and adhesive film for build-up, passive parts such as capacitors and active parts such as IC chips are embedded in so-called electronic parts. It can be used as an insulating material for a substrate. Among these, circuits such as hard printed wiring board materials, flexible wiring board resin compositions, build-up board interlayer insulation materials, etc., taking advantage of the characteristics of high heat resistance, especially low dielectric constant and low dielectric loss tangent It is preferably used for a substrate material and a semiconductor sealing material.

  Here, the circuit board of the present invention is manufactured by obtaining a varnish obtained by diluting a curable resin composition in an organic solvent, laminating a varnish formed in a plate shape with a copper foil, and heating and pressing. Is. Specifically, for example, to produce a hard printed wiring board, the varnish-like curable resin composition containing the organic solvent is further varnished by adding an organic solvent, and this is impregnated into a reinforcing base material. A method of obtaining the prepreg of the present invention produced by semi-curing, and laminating a copper foil on the prepreg and heating and press-bonding may be mentioned. 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. If this method is described in further detail, first, the varnish-like curable resin composition is heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., thereby being a prepreg which is a cured product. Get. At this time, the mass ratio of the curable resin composition to be used and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by 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 curable resin composition of the present invention, an active ester resin, an epoxy resin, and an organic solvent are blended, and using a coating machine such as a reverse roll coater or a comma coater, electrical insulation Apply to film. Subsequently, it heats at 60-170 degreeC for 1 to 15 minutes using a heating machine, volatilizes a solvent, and B-stages an adhesive composition. Next, the metal foil is thermocompression bonded to the adhesive 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 adhesive composition film after finally curing is preferably in the range of 5 to 100 μm.

  As a method for obtaining an interlayer insulating material for build-up substrates from the curable resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler, etc., is spray-coated on a wiring board on which a circuit is formed. After applying using a curtain coating 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. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  Next, in order to produce a semiconductor sealing material from the curable resin composition of the present invention, an active ester resin (A), an epoxy resin (B), and a compounding agent such as an inorganic filler are extruded as necessary. , Kneading, rolling, etc., and sufficient melt mixing until uniform. At that time, silica is usually used as the inorganic filler. In that case, by blending the inorganic filler in the curable resin composition in a proportion of 70 to 95% by mass, the semiconductor encapsulation of the present invention is performed. Become a material. For semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device which is a molded product. The method of obtaining is mentioned.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  When the curable resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.), and simultaneously with the lamination of the circuit board, It is important to show fluidity (resin flow) that allows resin filling in via holes or through holes present in a circuit board, 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 curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film (Y), Further, it can be produced by drying the organic solvent by heating or blowing hot air to form the layer (X) of the curable resin composition.

  The thickness of the formed layer (X) 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 layer (X) in this invention 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 support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) 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 (X) is protected by a protective film, after peeling these layers ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. 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.

Lamination 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), and air pressure. Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  The method for obtaining the cured product of the present invention may be based on a general curing method for a curable resin composition, but for example, the heating temperature condition may be appropriately selected depending on the kind of curing agent to be combined and the use. However, what is necessary is just to heat the composition obtained by the said method in the temperature range about 20-250 degreeC.

  Therefore, by using the epoxy resin, the solvent solubility of the epoxy resin is dramatically improved, and when it is made into a cured product, there is little change in heat resistance after the heat history, and a low thermal expansion coefficient can be expressed. Applicable to printed wiring board materials. In addition, the epoxy resin can be easily and efficiently manufactured by the manufacturing method of the present invention, and a molecular design corresponding to the target level of performance described above becomes possible.

  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 are as follows.
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
In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer, 144 parts by mass of α-naphthol (1.00 mol), 72 parts by mass of β-naphthol (0.50 mol), 37% by mass 142 parts by mass (1.75 mol) of an aqueous formaldehyde solution, 150 parts by mass of isopropyl alcohol, and 24 parts by mass (0.3 mol) of a 49% aqueous sodium hydroxide solution were added and stirred at room temperature while blowing nitrogen. Then, it heated up at 80 degreeC and stirred for 2 hours. After completion of the reaction, 40 parts by mass of first sodium phosphate was added to neutralize, then 600 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) was added, and washing was repeated 3 times with 150 parts by mass of water. After that, it was dried under heating under reduced pressure to obtain 200 parts by mass of the polycondensate (a-1). The obtained polycondensate (a-1) had a hydroxyl equivalent of 158 g / equivalent.

  Next, 158 parts by mass of the polycondensate (a-1) and 270 parts by mass of MIBK were charged into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer, and the system was purged with nitrogen under reduced pressure and dissolved. . Next, 138 parts by mass (0.98 mol) of benzoyl chloride was charged, and then 0.55 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while purging with nitrogen gas, and 20% hydroxylation was performed. 196 parts by mass of an aqueous sodium 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 MIBK 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, moisture was removed by decanter dehydration, and subsequently MIBK was removed by dehydration under reduced pressure to obtain 240 parts by mass of an active ester resin (A-1). A GPC chart of the active ester resin (A-1) is shown in FIG. The functional group equivalent based on the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group of the active ester resin (A-1) calculated from the charging ratio is 259 g / equivalent, and the polycondensate (a- The esterification rate of 1) with respect to the phenolic hydroxyl group was 98%. The content of the component corresponding to the trimer (x1) calculated from the GPC chart is 19.1%, the content of the component corresponding to the dimer (x2) is 3.3%, and the calixarene The content of the component corresponding to the compound (x3) was 38.3%, and the content of the component corresponding to the high molecular weight product (x4) was 35.4%.

Example 2
144 parts by mass (1.00 mol) of β-naphthol, 162 parts by mass (2.00 mol) of a 37% by mass aqueous formaldehyde solution, 250 parts by mass of isopropyl alcohol, and 33 parts by mass of an aqueous solution of 49% sodium hydroxide (0. It reacted like Example 1 except having changed to 4 mol), and obtained 290 mass parts of polycondensates (a-2). The obtained polycondensate (a-2) had a hydroxyl group equivalent of 153 grams / equivalent.

  Subsequently, it reacted like Example 1 except having changed into 153 mass parts of polycondensates (a-2), 98.4 mass parts (0.70 mol) of benzoyl chloride, and 140 mass parts of 20% sodium hydroxide aqueous solution. 200 parts by mass of an active ester resin (A-2) was obtained. The functional group equivalent based on the total number of functional groups of the carbonyloxy group and phenolic hydroxyl group of the active ester resin (A-2) calculated from the charging ratio is 226 g / equivalent, and the polycondensate (a- The esterification rate with respect to the phenolic acid group of 2) was 70%. The content of the component corresponding to the trimer (x1) calculated from the GPC chart is 24.1%, the content of the component corresponding to the dimer (x2) is 5.5%, and the calix The content of the component corresponding to the arene compound (x3) was 7.4%, and the content of the component corresponding to the high molecular weight product (x4) was 62.0%.

Comparative Synthesis Example 1
The reaction was performed in the same manner as in Example 2 except that the polycondensate (a-1) was changed to 105 parts by mass of phenol novolac resin (“TD-2090” manufactured by DIC), and 199 masses of active ester resin (A′-1) was obtained. I got a part. The functional group equivalent of this active ester resin (A′-1) was 210 g / equivalent from the charging ratio.

Examples 3 and 4 and Comparative Example 1
In accordance with the formulation shown in Table 1 below, “850-S” (bisphenol A type epoxy resin, epoxy equivalent: 187 g / eq) manufactured by DIC as the epoxy resin, and the active ester (A-1), (A-2) as the curing agent ) Or (A′-1), 0.5 phr of dimethylaminopyridine is added as a curing accelerator, and methyl ethyl ketone is finally added so that the nonvolatile content (N.V.) of each composition is 58 mass%. And adjusted. This was transferred to an aluminum petri dish and dried at 120 ° C. to remove methyl ethyl ketone to obtain a semi-cured product. Next, the semi-cured product is placed in a 15 cm × 15 cm × 2 mm mold and vacuum press-molded (temperature conditions: 200 ° C., pressure: 40 kg / cm 2, molding time: 1.5 hours) to obtain a plate-shaped cured product. It was. Using this as a test piece, the following various evaluations were performed. The results are shown in Table 1.

<Heat resistance change due to thermal history (amount of change in heat resistance: ΔTg): DMA (Tg difference between first measurement and second measurement)>
Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric, rectangular tension method; frequency 1 Hz, temperature rising rate 3 ° C./min), elastic modulus change twice under the following temperature conditions Was measured at the temperature (Tg) at which the tan δ was maximized (the tan δ change rate was the largest).
Temperature conditions 1st measurement: temperature rise from 35 ° C. to 275 ° C. at 3 ° C./min 2nd measurement: temperature rise from 35 ° C. to 330 ° C. at 3 ° C./min Each obtained temperature difference was evaluated as ΔTg.

<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.

Abbreviations in Table 1 are as follows.
850-S: “850-S” manufactured by DIC (bisphenol A type epoxy resin, epoxy equivalent: 187 g / eq)

Claims (9)

a reaction product of a polycondensate (a) of an α-naphthol compound, a β-naphthol compound and formaldehyde with a monocarboxylic acid compound or a halide (b) thereof,
The following structural formula (1)

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z represents a benzoyl group or 1 to 4 carbon atoms. Benzoyl group, naphthoyl group, and naphthoyl group nucleus-substituted with 1 to 3 of alkyl groups having 1 to 4 carbon atoms, acyl having 2 to 6 carbon atoms An ester-forming structural site (z1) selected from the group consisting of groups, or a hydrogen atom (z2). ]
A trimer (x1) represented by:
The following structural formula (2)

[Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and Z represents a benzoyl group or 1 to 4 carbon atoms. Benzoyl group, naphthoyl group, and naphthoyl group nucleus-substituted with 1 to 3 of alkyl groups having 1 to 4 carbon atoms, and 2 to 6 carbon atoms. An ester-forming structural site (z1) selected from the group consisting of acyl groups, or a hydrogen atom (z2). ]
A dimer (x2) represented by the formula, wherein the content of the trimer (x1) is a ratio of 15 to 35% in terms of area ratio in GPC measurement, and the dimer The content ratio of (x2) is a ratio that is in the range of 1 to 25% in the area ratio in GPC measurement, and at least one of X included in the trimer (x1) and the dimer (x2) One of the ester forming structural sites (z1) is an active ester resin. In addition to the trimer (x1) and the dimer (x2), the following structural formula (3)

[Wherein Z is a benzoyl group, a benzoyl group nucleosubstituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, a naphthoyl group, or 1 to 3 alkyl groups with 1 to 4 carbon atoms. A nucleus-substituted naphthoyl group, an ester-forming structural site (z1) selected from the group consisting of an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2), wherein R ¹ and R ² are each independently A hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms are shown, and n is a repeating unit and is an integer of 2 to 10. ]
In which the content ratio of the trimer (x1) is in the range of 15 to 35% in terms of area ratio in GPC measurement, and the dimer (x2 ) Is a ratio in which the area ratio in GPC measurement is in the range of 1 to 25%, and the content ratio of the calixarene compound (x3) is in the ratio in which the area ratio in GPC measurement is in the range of 1 to 40%. And an active ester resin in which at least one of X of the trimer (x1), the dimer (x2), or the calixarene compound (x3) is the ester-forming structural site (z1). 2. The active ester resin according to claim 1, wherein the functional group equivalent based on the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group in the active ester resin is in the range of 190 to 300 g / eq. A curable resin composition comprising the active ester resin according to any one of claims 1 to 3 and an epoxy resin as essential components. A cured product obtained by curing reaction of the curable resin composition according to claim 4. The semiconductor sealing material which consists of a curable resin composition of Claim 4 which contains an inorganic filler in the ratio used as 70-95 mass% in a composition further in addition to the said active ester resin and the said epoxy resin. A prepreg obtained by impregnating a reinforcing substrate with the curable resin composition according to claim 4 diluted in an organic solvent, and semi-curing the resulting impregnated substrate. A circuit board obtained by obtaining a varnish obtained by diluting the curable resin composition according to claim 4 in an organic solvent, and heating and press-molding a varnish shaped into a plate shape and a copper foil. A build-up film, wherein the curable resin composition according to claim 4 diluted with an organic solvent is applied onto a substrate film and dried.

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