JP2014024977A - Curable resin composition, cured product and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition having excellent heat resistance, low heat expansion coefficient and less change in heat resistance after heat history; a cured product obtained by curing this; and a printed wiring board.SOLUTION: A curable resin composition contains an epoxy resin (A) and a phenol resin (B), where the epoxy resin (A) contains a trimer represented by the structural formula (1) and a dimer having no naphthylmethylene group in the structural formula as essential components, and the phenol resin (B) contains a naphthol novolak resin and a naphthol as essential components.

Description

  The present invention relates to a curable composition in which the obtained cured product has excellent heat resistance, a low thermal expansion coefficient, and a small change in heat resistance after heat history, a cured product obtained by curing the cured product, and a printed wiring board.

  Compositions composed of epoxy compounds and phenolic compounds are widely used as insulating materials for semiconductor encapsulants and printed wiring boards because their cured products are excellent in heat resistance, moisture resistance, solder resistance, insulation, and the like.

  Among these, for printed wiring board applications, with the trend toward miniaturization and high performance of electronic equipment, it is required to realize high-density wiring by narrowing the wiring pitch, and as a semiconductor mounting method corresponding to this, Instead of the conventional wire bonding method, a flip chip connection method in which a semiconductor device and a wiring board are joined by solder balls has become the mainstream. In this flip-chip connection method, solder balls are placed between the wiring board and the semiconductor, and the whole is heated to reflow and join the solder. Therefore, the insulating material for the wiring board has only high heat resistance. In addition, more advanced performance is required such as small expansion when heated and small change in heat resistance after heat history.

  As a material particularly excellent in heat resistance, for example, a naphthol resin obtained by reacting naphthol and formaldehyde is known (see Patent Document 1 below).

  The naphthol resin described in Patent Document 1 has a higher chemical skeleton rigidity than a general phenol novolac resin. Therefore, when this resin is used as an epoxy resin curing agent, the heat resistance of the cured product is higher. However, it did not meet the ever-increasing demand level. Further, since the coefficient of thermal expansion is high and the heat resistance change after the thermal history is large, it does not have sufficient performance as a wiring board material.

  In addition, as a technique using a naphthol-based resin as a curing agent for an epoxy resin, for example, in Patent Document 2 below, a semiconductor encapsulating material can be obtained by using a naphthol novolak in which an excessive amount of a binuclear body and a trinuclear body exists. As described above, a technique has been disclosed that achieves low melt viscosity and improves workability. However, the naphthol resin described in Patent Document 2 does not exhibit sufficient heat resistance because it is easily decomposed under high heat conditions, and has a large thermal expansion coefficient and heat resistance change after heat history.

JP 2007-31527 A JP 7-215902 A

  Therefore, the problem to be solved by the present invention is that the obtained cured product is excellent in heat resistance, has a low thermal expansion coefficient, and has a small heat resistance change after heat history, and is obtained by curing this. It is providing a hardened | cured material and a printed wiring board.

  As a result of intensive studies to solve the above problems, the present inventors have used polyglycidyl ether of a naphthol novolak resin as a main agent, and an epoxy resin containing a trimer and a dimer having a specific structure, When a mixture of a naphthol resin having a relatively high molecular weight obtained by reacting a naphthol compound and formaldehyde as a curing agent and a specific amount of a free naphthol compound is used, the cured product has very high heat resistance. And it discovered that a thermal expansion coefficient was low and the heat resistance change after a heat history became small, and came to complete this invention.

That is, the present invention is a curable resin composition containing an epoxy resin (A) and a phenol resin (B), wherein the epoxy resin (A) is
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、Ｇはグリシジル基を表す。）
で表される３量体（ａ１）と、
下記構造式（２）

(In the formula, 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 G represents a glycidyl group.)
A trimer (a1) 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、Ｇはグリシジル基を表す。）
で表される２量体（ａ２）とを必須の成分として含有するものであり、かつ、前記フェノール樹脂（Ｂ）が、
下記一般式（ｉ）

(In the formula, 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 G represents a glycidyl group.)
And the dimer (a2) represented by the formula (2) as an essential component, and the phenol resin (B):
The following general formula (i)

（式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、アルキル基、アルコキシ基を表し、ｎは繰り返し単位であって１以上の整数である。）
で表されるナフトールノボラック樹脂（ｂ１）と、
下記一般式（ｉｉ）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and n is a repeating unit and is an integer of 1 or more.)
A naphthol novolac resin (b1) represented by:
The following general formula (ii)

（式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子、アルキル基、アルコキシ基を表す。）
で表される化合物（ｂ２）とを必須の成分として含有するものであることを特徴とする硬化性樹脂組成物に関する。

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an alkoxy group.)
And a compound (b2) represented by formula (b2) as an essential component.

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

  The present invention further relates to a printed wiring board obtained by impregnating a reinforcing base material with a varnish composition obtained by further blending an organic solvent with the curable composition, and stacking a copper foil and heat-pressing it.

  According to the present invention, the cured product from which the obtained cured product is obtained has excellent heat resistance, a low thermal expansion coefficient, and a small heat resistance change after heat history, and a cured product obtained by curing this. Products and printed wiring boards can be provided.

1 is a GPC chart of the epoxy resin (A-1) obtained in Production Example 1. FIG. FIG. 2 is a ¹³ C-NMR chart of the epoxy resin (A-1) obtained in Production Example 1. FIG. 3 is an MS spectrum of the epoxy resin (A-1) obtained in Production Example 1. FIG. 4 is a GPC chart of the epoxy resin (A-2) obtained in Production Example 2. FIG. 5 is a GPC chart of the epoxy resin (A-3) obtained in Production Example 3. FIG. 6 is a GPC chart of the epoxy resin (A-4) obtained in Production Example 4. FIG. 7 is a ¹³ C-NMR chart of the epoxy resin (A-4) obtained in Production Example 4. FIG. 8 is an MS spectrum of the epoxy resin (A-4) obtained in Production Example 4. FIG. 9 is a GPC chart of the phenol resin (B-1) obtained in Production Example 5. FIG. 10 is a GPC chart of the phenol resin (B-2) obtained in Production Example 6. FIG. 11 is a GPC chart of the phenol resin (B-3) obtained in Production Example 7. FIG. 12 is a ¹³ C-NMR chart of the phenol resin (B-3) obtained in Production Example 7. FIG. 13 is an FD-MS spectrum of the phenol resin (B-3) obtained in Production Example 7. FIG. 14 is a GPC chart of the phenol resin (B′-1) obtained in Comparative Production Example 1. FIG. 15 is a GPC chart of the phenol resin (B′-2) obtained in Comparative Production Example 2.

Hereinafter, the present invention will be described in detail.
The epoxy resin (A) of the present invention has 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、Ｇはグリシジル基を表す。）
で表される３量体（ａ１）と、
下記構造式（２）

(In the formula, 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 G represents a glycidyl group.)
A trimer (a1) 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、Ｇはグリシジル基を表す。）
で表される２量体（ａ２）とを必須の成分として含有するものである。

(In the formula, 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 G represents a glycidyl group.)
It contains the dimer (a2) represented by these as an essential component.

  More specifically, for example, an epoxy resin obtained by polyglycidyl etherification of a polycondensate of an α-naphthol compound, a β-naphthol compound, and formaldehyde can be given.

  In the present invention, since the epoxy resin (A) contains the trimer (a1), the orientation at the molecular level is high, and the cured product exhibits excellent low thermal expansibility, and the trimer ( a1) Since the reactivity of itself is high, there is little change in heat resistance after heat history in the cured product, and the material has little change in physical properties after reflow in printed wiring board applications. Especially, since it becomes resin more excellent in solvent solubility and hardened | cured material can obtain hardened | cured material with low thermal expansibility, the said trimer (a1) will be 15 to 35% by the area ratio in GPC measurement. It is preferable to contain by a ratio.

  Specifically, such trimer (a1) 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.

  Moreover, in this invention, since the said epoxy resin (A) contains the said dimer (a2), hardened | cured material becomes a thing with low thermal expansibility. Moreover, since it becomes an epoxy resin excellent in solvent solubility, it can be used as a varnish for a printed wiring board. Especially, since it is excellent in solvent solubility and low thermal expansibility, it is preferable to contain the said dimer (a2) in the ratio used as 1-25% by the area ratio in GPC measurement.

  In addition to the trimer (a1) and the dimer (a2), the epoxy resin of the present invention further includes the following structural formula (3).

（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、Ｇはグリシジル基を表し、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（ａ３）を含有することが、硬化物における熱膨張性がより低いものとなることから好ましい。中でも、エポキシ樹脂（Ａ）中ＧＰＣ測定における面積比率で１〜４０％となる割合で含有することが、硬化物における低線膨張性がより一層良好なものとなる点から好ましい。

(In the formula, 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, G represents a glycidyl group, and n represents a repeating group. It is a unit and is an integer of 2 to 10.)
It is preferable that the calixarene compound (a3) represented by the formula (1) is contained since the thermal expansion in the cured product is lower. Especially, it is preferable to contain in the ratio which becomes 1 to 40% by the area ratio in GPC measurement in an epoxy resin (A) from the point from which the low linear expansion property in hardened | cured material becomes still more favorable.

Here, R ¹ and R ² in the structural formula (3) are synonymous with those in the structural formula (1). Although the repeating unit n is an integer of 2 to 10, n is preferably 4 from the viewpoint that the low linear expansion in the cured product of the epoxy resin (A) of the present invention is further improved.

In the present invention, the content of the trimer (a1), the dimer (a2), and the calixarene compound (a3) in the epoxy resin (A) 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 (A) of the present invention.
<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).

  The epoxy resin (A) of the present invention may contain a high molecular weight component (a4) in addition to the trimer (a1), the dimer (a2), and the calixarene compound (a3). Good.

  Such a high molecular weight component (a4) is a high molecular weight component excluding the above (a1) to (a3) in the epoxy resin (A) of the present invention, and specifically, the following structural formula (I)

（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、Ｇはグリシジル基を表す。）
で表される構造ユニット（Ｉ）と、
下記、構造式（ＩＩ）

(In the formula, 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 G represents a glycidyl group.)
A structural unit (I) represented by:
Structural formula (II) below

（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、Ｇはグリシジル基を表し、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エポキシ樹脂である。

(In the formula, 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, G represents a glycidyl group, and m represents a repeating group. Unit, an integer greater than or equal to 0.)
And an epoxy resin having a basic structure that is knotted by a methylene bond and has a high molecular weight.

  The dimer (a2), the trimer (a1), and the calixarene compound (a3) are detected in order of the retention time by GPC measurement, and the high molecular weight component (a4) is detected by the calixarene compound (a3). Therefore, it is a component detected in a region having a short holding time. The proportion of the high molecular weight component (a4) in the epoxy resin (A) is an area ratio in GPC measurement, and is in the range of 40 to 75% by mass because the solvent solubility of the epoxy resin (A) is excellent. preferable. The specific structure of the high molecular weight component (a4) includes a resin structure (a4-1) in which the structural unit (I) and the structural unit (II) are alternately bonded through a methylene bond, and the structure. The resin structure (a4-2) in which the structural unit (II) is bonded to both ends of the unit (I) via a methylene bond is exemplified. In the present invention, the resin structure (a4-2) is selected from the viewpoint of low thermal expansion. What has is preferable. In the resin structure (a4-2), the structural unit (II) is located at both ends of the structure as described above, but is bonded to the methylene bond among the two bonds of the structural unit (II). 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, when the other novolak resin is used in combination, the high molecular weight component (a4) 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 epoxy resin (A) finally obtained.

  The epoxy resin (A) of the present invention described in detail above preferably has a softening point in the range of 95 to 140 ° C. from the viewpoint of excellent solvent solubility of the epoxy resin (A) itself. The molecular weight of (a4) may be appropriately adjusted so that the softening point of the epoxy resin falls within the above range. The softening point is particularly preferably in the range of 100 to 135 ° C. from the viewpoint that the low thermal expansion property and the solvent solubility can be highly combined.

  The epoxy resin (A) of the present invention preferably has an epoxy equivalent in the range of 210 to 300 g / eq from the viewpoint of good low thermal expansion of the cured product, particularly in the range of 220 to 260 g / eq. It is preferable that

The epoxy resin (A) of the present invention described in detail above can be produced by, for example, 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 an α-naphthol compound is added and reacted in the presence of formaldehyde to obtain a naphthol resin (step 1). A method of obtaining the target epoxy resin (A) by reacting the obtained naphthol resin with epihalohydrin (step 2).
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 naphthol resin (step 1), and then the resulting naphthol resin fat is reacted with epihalohydrin. (Step 2) to obtain the target epoxy resin (A).

  In the present invention, in the step 1 of the method 1 or 2, by using an alkali catalyst as a reaction catalyst and using a small amount of an organic solvent relative to the raw material components, the trimer (a1), the 2 The abundance ratio of the monomer (a2) and the calixarene compound (a3) in the epoxy resin can be adjusted to a predetermined range, and the abundance ratio of the high molecular weight component 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. Of these, isopropyl alcohol is particularly preferred from the viewpoint of relatively high molecular weight of the polycondensate.

  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. The proportion of the trimer (a1), the dimer (a2), and the calixarene compound (a3) in the epoxy resin is in the range of 5 to 70 parts by mass per 100 parts by mass of the total mass. Is preferable because it is easy to adjust 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 the heat history in the finally obtained cured product of the epoxy resin (A) 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 epoxy resin (A) 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, in particular, low thermal expansion. From the viewpoint of excellent properties, the ratio is preferably 0.6 to 1.5 times the 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 using these in combination, the solvent solubility of the epoxy resin finally obtained can be dramatically improved. Can do. These phenol novolak resins and cresol novolak resins are preferably those having a softening point of 60 to 120 ° C. from the viewpoint that the solvent solubility can be improved without reducing the performance such as low linear expansion in the present invention.

  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 epoxy resin finally obtained when the number of aromatic nuclei in the resin is in the range of [1 / 0.06] to [1 / 0.36]. Preferably, the amount of formaldehyde used is 0.6 to 2.2 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 the amount be 0 times the amount, in particular, the range where the amount becomes 0.6 to 1.5 times the amount from the viewpoint of excellent balance between 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, Step 2 of Method 1 or Method 2 is a step of producing the target epoxy resin (A) by reacting the polycondensate obtained in Step 1 with epihalohydrin. Specifically, in the step 2, epihalohydrin is added in a ratio of 2 to 10 times (molar basis) with respect to the number of moles of the phenolic hydroxyl group in the polycondensate, and further the mole of the phenolic hydroxyl group. A method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding 0.9 to 2.0 times (molar basis) of the basic catalyst to the number is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. Alternatively, the solution may be separated and further separated to remove water and the epihalohydrin is continuously returned to the reaction mixture.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin (A) can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohol compounds such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples thereof include cellosolves such as cellosolve and ethyl cellosolve, ether compounds such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more kinds in order to adjust the polarity.

  After the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the epoxy resin used. After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent such as toluene and methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain the desired epoxy resin (A) of the present invention. it can.

  Next, the phenol resin (B) used in the present invention has the following general formula (i):

（式中、Ｒ^１及びＲ^２は、それぞれ独立的に水素原子、アルキル基、アルコキシ基を表し、ｎは繰り返し単位であって１以上の整数である。）
で表されるナフトールノボラック樹脂（ｂ１）と、
下記一般式（ｉｉ）

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and n is a repeating unit and is an integer of 1 or more.)
A naphthol novolac resin (b1) represented by:
The following general formula (ii)

（式中、Ｒ^１及びＲ^２は、それぞれ独立的に水素原子、アルキル基、アルコキシ基を表す。）
で表される化合物（ｂ２）とを必須の成分として含有するものである。

(In the formula, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, or an alkoxy group.)
And (b2) as an essential component.

  In the phenol resin (B), the total peak area in the GPC measurement of n = 1 and n = 2 in the general formula (i) is in the range of 10 to 35% in the phenol resin (B), and By setting the average of n in the general formula (i) in the range of 3.0 to 7.0, a naphthol novolak resin having a high molecular weight and a wide molecular weight distribution is obtained, and thermal decomposition is suppressed, and the rigid skeleton of the naphthalene skeleton is formed. It is preferable because excellent heat resistance is expressed in combination with the heat resistance. Especially, the sum total of the peak areas in the GPC measurement of n = 1 body and n = 2 body in the general formula (i) is in the range of 20 to 35% in the phenol resin (B), and the average of n The range of 3.0 to 5.0 is preferable because the heat resistance of the cured product is improved.

  In addition, the content of the compound (b2) in the phenol resin (B) on the basis of the peak area in the GPC measurement reduces the viscosity of the phenol resin (B), and as a result, the curing reaction proceeds sufficiently, resulting in heat resistance. Since the cured | curing material which is excellent can be obtained, it is preferable that it is a ratio used as 1 to 6%. That is, the viscosity of the phenolic resin (B) can be reduced by adding or removing a mononaphthol compound that has been removed in order to avoid a decrease in heat resistance in a specific ratio, and further improving the curability. Therefore, a cured product that is more excellent in heat resistance can be obtained.

  The naphthol monomer such as the compound (b2) makes it possible to form a denser π stacking upon curing with the epoxy resin (A), and obtains a cured product excellent in low thermal expansion in addition to heat resistance. Contributes to curing. Furthermore, as a result of synergistically exhibiting the effect of increasing the density of such π stacking and the above-described viscosity reducing effect, the reaction rate of the curing reaction is high, and not only the heat resistance of the cured product is improved, The rate of change in heat resistance after the heat history can be reduced. In general, a composition containing a relatively low molecular weight component such as the trimer (a1), the dimer (a2) or the compound (b2) has a low viscosity, but has a high heat resistance of a cured product. Where there is a tendency to be inferior, by making the structure of each component specific, it is possible to obtain a composition that improves the reaction rate and reduces the viscosity but also has excellent heat resistance of the cured product.

Here, the area ratio in the total GPC measurement of the compound (b2) and n = 1 body and n = 2 body in the general formula (i) is the phenol resin of the present invention (B ) The area ratio between the total area and the sum of the peak areas of the compound (b2) and the n = 1 isomer and the n = 2 isomer in the general formula (i), specifically by the following method A value that is measured and calculated. Moreover, the average of n in the general formula (i) is a value calculated based on the result obtained by deriving the number average molecular weight by excluding the peak of the compound (b2) in the GPC measurement of the phenol resin (B). It is.
<GPC measurement conditions>
3) GPC: The 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 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).

<Calculation method of content rate of compound (b2) in phenol resin (B)>
It is a value calculated by measuring the phenol resin (B) under the above GPC measurement conditions and the ratio of the peak area of all the detected phenol resins to the peak area of the compound (b2).

<Calculation Method of Presence Ratio in Total Phenol Resin (B) of n = 1 Form and n = 2 Form in General Formula (i)>
The phenol resin (B) was measured under the above GPC measurement conditions, and all peak areas of the detected phenol resin (B) and the respective peak areas of n = 1 and n = 2 in the general formula (i) It is a value calculated by the ratio with the sum of.

<The calculation method of the average of n in the said general formula (i)>
The average of n in the general formula (i) was calculated by the following calculation formula from the number average molecular weight (Mn) obtained by measuring the phenol resin (B) under the above GPC measurement conditions and excluding the peak of the compound (b2). It is. In the following formula, “X” represents a molecular weight corresponding to n = 0 isomer in the general formula (i) [when the naphthol novolak resin (b1) is produced from the same compound as the compound (b2), the compound (b2 ) Molecular weight]. Moreover, in this invention, even if it is a case where the phenol novolak or alkylphenol novolak component (b3) mentioned later is contained, the average of n becomes a value calculated by the following formula.
n = (Mn-X) / (X + 12)

Here, as described above, R ¹ and R ² in the general formula (i) in the naphthol novolak resin (b1) are each independently a hydrogen atom, an alkyl group, or an alkoxy group. Here, examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, and a t-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, i- C1-C4 alkoxy groups, such as a propyloxy group and t-butyloxy group, are mentioned. In the present invention, R ¹ and R ² are particularly preferably a hydrogen atom, a methyl group, an ethyl group, or a methoxy group, and in particular, a hydrogen atom from the viewpoint of excellent heat resistance and low thermal expansion of the cured product. It is preferable.

  Further, the naphthol skeleton in the general formula (i) may be either an α-naphthol skeleton or a β-naphthol skeleton, but in the present invention, the α-naphthol skeleton has a remarkable effect of improving heat resistance. It is preferable from the point which becomes a thing. Further, the naphthol novolak resin (b1) is a naphthol novolak resin using the same compound as the compound (b2) as a raw material in the present invention, because it is excellent in solvent solubility, heat resistance of the cured product and low thermal expansion. preferable.

Next, R ¹ and R ² in the general formula (ii) in the compound (b2) are each independently a hydrogen atom, an alkyl group, or an alkoxy group, as described above. Here, examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, and a t-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, i- C1-C4 alkoxy groups, such as a propyloxy group and t-butyloxy group, are mentioned. In the present invention, R ¹ and R ² are particularly preferably a hydrogen atom, a methyl group, an ethyl group, or a methoxy group, and among them, the curability is good and the cured product is excellent in heat resistance and low thermal expansion. From the viewpoint, a hydrogen atom is preferable.

  The naphthol novolak resin (b1) and the compound (b2) described above can be used as the phenol resin (B) of the present invention by blending so that the area ratio in the latter GPC measurement is 1 to 6%. As described above, it is preferable to use, as the naphthol novolak resin (b1), a naphthol novolac resin using the same compound as the compound (b2) as a raw material. In this case, the following general formula (ii)

（式中、Ｒ^１及びＲ^２は、それぞれ独立的に水素原子、アルキル基、アルコキシ基を表す。）
で表される化合物（ｂ２）と、ホルムアルデヒド（ｆ）とを、酸触媒下に、生成物中の前記化合物（ｂ２）の残存量がＧＰＣ測定におけるピーク面積基準で１〜６％、生成物の軟化点が１１５〜１５０℃となるように反応させることを特徴とする本発明のフェノール樹脂組成物の製造方法（以下、これを「方法１」と略記する。）によって前記フェノール樹脂組成物を製造することが、工業的な生産性に優れると共に、混合物の均一性に優れ、低熱膨張性の改善効果がより顕著なものとなる点から好ましい。

(In the formula, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, or an alkoxy group.)
The amount of the compound (b2) in the product is 1 to 6% based on the peak area in GPC measurement under the acid catalyst, the compound (b2) represented by the formula (b2) and formaldehyde (f). The phenol resin composition is produced by a method for producing a phenol resin composition of the present invention (hereinafter, abbreviated as “Method 1”), wherein the reaction is performed so that the softening point is 115 to 150 ° C. It is preferable from the viewpoint that the industrial productivity is excellent, the uniformity of the mixture is excellent, and the effect of improving the low thermal expansion becomes more remarkable.

  In such method 1, the reaction ratio between the compound (b2) and formaldehyde (f) is such a ratio that the molar ratio [formaldehyde (f) / compound (b2)] is 0.6 to 0.8. Is preferable because a cured product having excellent heat resistance and low thermal expansion can be obtained.

  Examples of the formaldehyde source of formaldehyde (f) used in the above reaction include formalin, paraformaldehyde, trioxane and the like. Here, it is preferable that formalin is 30-60 mass% formalin from the point of water dilutability and workability | operativity at the time of manufacture.

  Examples of the acid catalyst used in the above reaction include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acid etc. are mentioned. The amount used is preferably in the range of 0.1 to 5% by weight with respect to the total weight of the charged raw materials.

  Moreover, it is preferable from the point which is excellent in the reactivity that the reaction temperature in the method 1 is the range of 80-150 degreeC.

  The phenol resin (B) containing the polycondensate (b1) and the compound (b2) obtained in this manner has a softening point in the range of 110 to 150 ° C. and fluidity and cured product in the composition. It is preferable from the viewpoint of excellent balance with heat resistance.

  In addition to the naphthol novolak resin (b1) and the compound (b2), the phenol resin composition of the present invention contains a phenol novolak or an alkylphenol novolak component (b3), which can further improve the rate of change in heat resistance of the cured product. It is preferable from the point.

  Here, the phenol novolak or alkylphenol novolak component (b3) (hereinafter abbreviated as “novolak component (b3)”) is the weight of phenol novolak or alkylphenol novolak (n) and the naphthols and formaldehyde. Condensates (b3 ′) can be mentioned, and in particular, the resin component containing the novolak (n) and the polycondensate (b3 ′) in an integrated manner is excellent in the effect of improving heat resistance and low thermal expansion. To preferred.

  Here, the proportion of the novolak component (b3) in the phenol resin composition is such that the total phenol skeleton in the novolak component (b3) with respect to the total naphthol skeleton in the polycondensate (b1) and the compound (b2). The proportion is preferably such that the phenol skeleton is 0.2 to 0.01 mol per mole of naphthol skeleton, since the effect of improving the heat resistance and low thermal expansion is remarkable in the cured product.

Here, the ratio of the number of moles of the phenol skeleton per mole of the naphthol skeleton is calculated by ¹³ C-NMR measurement, specifically, a value measured and calculated by the following method.
< ^13C -NMR measurement conditions>
¹³ C-NMR: Measurement conditions are as follows.
Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination)
Solvent: Dimethyl sulfoxide Pulse angle: 45 ° C pulse Sample concentration: 30 wt%
Integration count: 10,000 times

<Calculation method of ratio of moles of phenol skeleton per mole of naphthol skeleton>
When the phenol resin composition is measured under the above ¹³ C-NMR measurement conditions, it is detected between the integrated value (α) of the peak of the carbon atom to which the hydroxyl group detected between 145 ppm and 160 ppm is bonded and between 100 ppm and 140 ppm. The relationship of the integrated value (β) of the peaks of carbon atoms to which no hydroxyl group is bonded satisfies the following formula (1) and the following formula (2). Here, (X) represents the number of moles of the naphthol skeleton, and (Y) represents the number of moles of the phenol skeleton.

  Therefore, from the above formulas (1) and (2), the mole ratio (Y / X) of the phenol skeleton per mole of naphthol skeleton can be calculated by the following formula (3).

  As a method of blending the novolak component (b3) in the phenol resin composition of the present invention, specifically, when the phenol resin composition is produced, the following general formula (2)

（式中、Ｒ^１及びＲ^２は、それぞれ独立的に水素原子、アルキル基、アルコキシ基を表す。）
で表される化合物（ｂ２）と、ホルムアルデヒド（ｆ）と、フェノールノボラック又はアルキルフェノールノボラック成分（ｂ３）とを、酸触媒下に、生成物中の前記化合物（ｂ２）の残存量がＧＰＣ測定におけるピーク面積基準で１〜６％、生成物の軟化点が１１５〜１５０℃となるように反応させる方法（以下、これを「方法２」と略記する。）が挙げられる。本発明では、かかる方法２により、ノボラック成分（ｂ３）を含有するフェノール樹脂組成物を製造する場合、該フェノール樹脂組成物の工業的な生産性が良好なものとなると共に、該フェノール樹脂組成物の均一性に優れ、低熱膨張性の改善効果がより顕著なものとなる点から好ましい。

(In the formula, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, or an alkoxy group.)
The residual amount of the compound (b2) in the product is a peak in GPC measurement in the presence of a compound (b2) represented by the formula (b2), formaldehyde (f), and a phenol novolak or alkylphenol novolak component (b3). Examples include a method of reacting such that the softening point of the product is 115 to 150 ° C. on an area basis (hereinafter referred to as “method 2”). In the present invention, when the phenol resin composition containing the novolak component (b3) is produced by the method 2, the industrial productivity of the phenol resin composition is improved and the phenol resin composition is produced. It is preferable from the viewpoint that the uniformity of the resin is excellent and the effect of improving the low thermal expansion becomes more remarkable.

  Here, specific examples of the phenol novolak or alkylphenol novolak (b3) used in the method 2 include phenol novolak, cresol novolak, and t-butylphenol novolak. In the present invention, cresol novolac is preferable from the viewpoint of excellent flame retardancy. The phenol novolak or alkylphenol novolak (b3) has a softening point in the range of 60 to 120 ° C., and further has an average number of nuclei in the range of 3 to 10 by GPC measurement under the above conditions. In particular, the phenol resin composition obtained is preferable in that the fluidity of the phenol resin composition is kept high and the effect of improving flame retardancy and adhesion is good.

  The amount of phenol novolak or alkylphenol novolak (n) used in Method 2 is preferably 0.5 to 10% by mass in the raw material components. The raw material component described here refers to the total amount of the compound (b2), formaldehyde (f) and phenol novolak or alkylphenol novolak (b3). On the other hand, the reaction ratio between the compound (b2) and formaldehyde (f) is the ratio at which the molar ratio [formaldehyde (f) / compound (b2)] is 0.6 to 0.8, as in Method 1. It is preferable from the point which is excellent in a flame retardance and adhesiveness.

  The acid catalyst used in Method 2 is the same as in Method 1, such as inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, and trifluoride. Examples thereof include Lewis acids such as boron, anhydrous aluminum chloride, and zinc chloride. The amount used is preferably in the range of 0.1 to 5% by weight with respect to the total weight of the charged raw materials.

  The reaction temperature in Method 2 is preferably in the range of 80 to 150 ° C. from the viewpoint of excellent reactivity.

  Thus, it is preferable that the phenol resin composition manufactured by the method 2 has a softening point in the range of 110 to 150 from the viewpoint of excellent balance between fluidity in the composition and heat resistance in the cured product.

  The blending ratio of the epoxy resin (A) and the phenol resin (B) in the curable composition of the present invention is not particularly limited, but the obtained cured product is superior in heat resistance. The total of phenolic hydroxyl groups contained in the g phenol resin (B) is in a range of 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups in the epoxy resin (A). It is preferable.

The curable composition of the present invention uses the above-described phenol resin (B) as an epoxy resin curing agent, and optionally uses another epoxy resin curing agent (B ′) as needed. May be. Examples of other curing agents for epoxy resin that can be used here include various known curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And 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. Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensation Novolac resin, naphthol-cresol co-condensed novolak 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 (polyhydric phenol compound in which phenol nucleus is linked with melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring-modified novo Examples thereof include polyhydric phenol compounds such as rack resin (polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

  When using the other curing agent for epoxy resin (B ′) described above, the amount used is equivalent to the active hydrogen in the curing agent for epoxy resin (B ′) and the phenolic hydroxyl group in the phenol resin (B). The ratio (active hydrogen / hydroxyl group) is preferably in the range of 1/10 to 5/1.

  In the present invention, an epoxy compound (A ′) other than the epoxy resin (A) may be used in combination. It is preferable that the usage-amount of another epoxy compound (A ') is the range used as 5-50 mass% in all the epoxy components, for example.

  As the epoxy compound (A ′) that can be used here, various epoxy resins can be used. For example, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins, Biphenyl type epoxy resins such as tetramethylbiphenyl type epoxy resins; phenol novolac type epoxy resins, cresol novolak type epoxy resins, bisphenol A novolac type epoxy resins, and epoxy compounds of condensates of phenolic compounds and aromatic aldehydes having phenolic hydroxyl groups , Novolac type epoxy resins such as biphenyl novolac type epoxy resins; triphenylmethane type epoxy resins; tetraphenylethane type epoxy resins; dicyclopentadiene-phenol addition reaction type Epoxy resins; phenol aralkyl type epoxy resins; phosphorus-containing epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Here, as the phosphorus atom-containing epoxy resin, epoxidized product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones Epoxidized phenolic resin obtained by reacting phenolic resin, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol noboc type epoxy resin with HCA, bisphenol A type epoxy resin and HCA Examples thereof include an epoxy resin obtained by modification with a phenol resin obtained by reacting with quinones.

  In this invention, a hardening accelerator can also be used together suitably 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 sealing material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that 2-ethyl-4-methylimidazole is used for imidazole compounds, and triphenylphosphine is used for phosphorus compounds. For fins and tertiary amines, 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferred.

  When adjusting the curable composition of this invention explained in full detail above to the varnish for printed wiring boards, etc., it is preferable to mix | blend an organic solvent (C) other than said each component. 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 less, 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, examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, and cellosolve. It is preferable to use carbitol solvents such as butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, and the non-volatile content is 30 to 60% by mass. It is preferable to use in proportions.

  In order to further improve the flame retardancy, the curable composition of the present invention may contain a non-halogen flame retardant that substantially does not contain a halogen atom, for example, in printed wiring board applications.

  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 thermosetting resins such as phenolic resin, and (iii) thermosetting of phenolic resin 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 phosphorus-based flame retardant, other components of the curable composition, and the desired degree of flame retardancy. For example, epoxy components, curing agents, non- and In 100 parts by mass of the curable composition in which all other fillers and additives are blended, when red phosphorus is used as a non-halogen flame retardant, it may be blended in the range of 0.1 to 2.0 parts by mass. Preferably, when an organic phosphorus compound is used, it is preferably blended in the range of 0.1 to 10.0 parts by mass, and particularly preferably in the range of 0.5 to 6.0 parts by mass.

  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 (Ii) co-condensates of phenolic compounds such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine and formaldehyde; ) A mixture of the cocondensate of (ii) and a phenol 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 done.

  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 depending on the type of the nitrogen-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass, especially in 0.1 to 10 parts by mass, in 100 parts by mass of the curable composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 5 parts by mass.

  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 component, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable 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, Shipley (Bokusui Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3-based, ZnO-P2O5-MgO-based, P2O5-B2O3-PbO-MgO-based, Examples thereof include glassy compounds such as P—Sn—O—F, PbO—V 2 O 5 —TeO 2, Al 2 O 3 —H 2 O, and lead borosilicate.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.5 to 50 parts by mass, particularly 5 to 30 parts by mass, in 100 parts by mass of the curable composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to blend in the range of 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-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.005 to 10 parts by mass in 100 parts by mass of the curable composition containing all of the epoxy component, curing agent, non-halogen flame retardant and other fillers and additives.

  An inorganic filler can be mix | blended with the curable 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 in the range of 0.5 to 100 parts by mass in 100 parts by mass of the curable 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 composition of this invention as needed.

  The curable composition of this invention is obtained by mixing each above-mentioned component uniformly. The curable composition of the present invention in which an epoxy component, a curing agent and, 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.

  Applications for which the curable composition of the present invention is used include printed wiring board materials, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, and adhesive films for build-up. Among these various applications, in printed circuit boards, insulating materials for electronic circuit boards, and adhesive films 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, it is preferable to use for the printed wiring board material and the adhesive film for buildup from the characteristics, such as high heat resistance and a flame retardance.

  Here, in order to produce a printed circuit board from the curable composition of the present invention, a resin composition blended with the organic solvent (C) and varnished is impregnated into a reinforcing base material, and a copper foil is overlaid and heated. The method of making it crimp is 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. More specifically, the varnish-like curable composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., so that a prepreg as a cured product is obtained. obtain. Although it does not specifically limit as a mass ratio of the curable composition used at this time and a reinforcement base material, Usually, it is preferable to prepare so that the resin part 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 desired printed circuit board can be obtained.

  When the curable composition of the present invention is used as a resist ink, for example, a cationic polymerization catalyst is used as a catalyst for the curable composition, and a pigment, talc, and filler are further added to form 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.

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

  As a method for obtaining an interlayer insulating material for a build-up substrate from the curable composition of the present invention, for example, the curable composition appropriately blended with rubber, filler and the like is applied to a wiring substrate on which a circuit is formed by a spray coating method, a curtain After applying using a 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. Moreover, a roughened surface is formed by heat-pressing a copper foil with resin obtained by semi-curing the curable composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to produce a build-up substrate by omitting this process.

  The method for producing an adhesive film for buildup from the curable composition of the present invention is, for example, applied for a multilayer printed wiring board by applying the curable composition of the present invention on a support film to form a resin composition layer. The method of setting it as an adhesive film is mentioned.

  When the curable composition of the present invention is used for an adhesive film for build-up, the adhesive film is softened under a lamination temperature condition (usually 70 ° C. to 140 ° C.) in a vacuum laminating method. 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 above-mentioned adhesive film is prepared by preparing the varnish-like curable composition of the present invention, and then applying the varnish-like composition to the surface of the support film (y). 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 curable 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, a 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 with 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.

  The lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 104 N / m 2), and the air pressure is 20 mmHg (26 It is preferable to laminate under a reduced pressure of 0.7 hPa or less.

  What is necessary is just to heat the composition obtained by the said method in the temperature range about 20-250 degreeC as a method of obtaining the hardened | cured material of this invention.

Next, the present invention will be described in more detail with reference to examples and comparative examples.
"" Is based on mass unless otherwise specified. The softening point, 13C-NMR, GPC and MS were measured under the following conditions.

1) Softening point measurement method: JIS K7234

2) 13C-NMR: Measurement conditions are as follows.
Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination)
Solvent: Dimethyl sulfoxide pulse angle: 45 ° C pulse Sample concentration: 30 wt%
Integration count: 10,000 times

3) GPC: The 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 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).

4) MS: Double Density Mass Spectrometer AX505H (FD505 manufactured by JEOL Ltd.)
H)

Production Example 1 Production of Epoxy Resin (A-1) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 144 parts of β-naphthol (1.0 mol), 150 parts of isopropyl alcohol, The mixture was charged with 130 parts (1.6 mol) of 37% formalin aqueous solution and 41 parts (0.5 mol) of 49% sodium hydroxide, heated from room temperature to 80 ° C. with stirring, and stirred at 80 ° C. for 1 hour. Subsequently, 144 parts (1.0 mol) of α-naphthol was charged and further stirred at 80 ° C. for 1 hour. After completion of the reaction, 60 parts by mass of first sodium phosphate was added to neutralize, 600 parts of methyl isobutyl ketone was added, washing was repeated 3 times with 150 parts by mass of water, and then dried under heating and reduced pressure to obtain a naphthol resin ( a-1) 290 parts by mass were obtained. The obtained naphthol resin (a-1) had a hydroxyl group equivalent of 153 g / equivalent.

  Next, 153 parts by mass of naphthol resin (a-1) obtained by the above reaction (1.0 equivalent of hydroxyl group) and 463 parts by mass of epichlorohydrin (5) while purging a flask equipped with a thermometer, a condenser, and a stirrer with nitrogen gas purge. 0.0 mol) and 53 parts by mass of n-butanol were charged and dissolved while stirring. After the temperature was raised to 50 ° C., 220 parts by mass of a 20% aqueous sodium hydroxide solution (1.10 mol) was added over 3 hours, and the reaction was further continued at 50 ° C. for 1 hour. After completion of the reaction, stirring was stopped, the aqueous layer accumulated in the lower layer was removed, stirring was resumed, and unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. Then, 300 parts by mass of methyl isobutyl ketone and 50 parts by mass of n-butanol were added to the resulting crude epoxy resin and dissolved. Further, 15 parts by mass of a 10% by mass sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with 100 parts by mass of water was repeated three times until the pH of the cleaning solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 200 parts by mass of the desired epoxy resin (A-1). The obtained epoxy resin (A-1) has an epoxy equivalent of 234 g / equivalent and a softening point of 113 ° C., FIG. 1 shows a GPC chart, FIG. 2 shows an NMR chart, and FIG. 3 shows a MASS chart. From the GPC chart, the content of the trimer (a1) is 25.3%, the content of the dimer (a2) is 5.3%, the content of the calixarene compound (a3) is 7.4%, and the high molecular weight The content rate of a body (a4) was 62.0%.

Production Example 2 Production of Epoxy Resin (A-2) 72 parts (0.5 mol) of β-naphthol, 130 parts of isopropyl alcohol, 142 parts of a 37% formalin aqueous solution (1.75 mol), 24 parts of 49% sodium hydroxide ( Except having changed into 0.3 mol), it carried out similarly to Example 1, and obtained 200 mass parts of epoxy resins (A-2). The obtained epoxy resin (A-2) has an epoxy equivalent of 242 g / equivalent and a softening point of 134 ° C., and a GPC chart is shown in FIG. From the GPC chart, the content of the trimer (a1) is 15.8%, the content of the dimer (a2) is 3.0%, the content of the calixarene compound (a3) is 33.0%, and the high molecular weight The content rate of body (a4) was 48.2%.

Production Example 3 Production of Epoxy Resin (A-3) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 115 parts (0.80 mol) of β-naphthol and 173 parts of α-naphthol (1.20 mol), softening point 75 ° C. (B & R method) 54 parts by mass of cresol novolac resin (number of moles of cresol skeleton: 0.45 mol), 150 parts of isopropyl alcohol, 135 parts of 37% formalin aqueous solution (1.66 Mol) and 5 parts (0.06 mol) of 49% sodium hydroxide, the temperature was raised from room temperature to 80 ° C. with stirring, and the mixture was stirred at 80 ° C. for 2 hours. After completion of the reaction, 10 parts by mass of sodium phosphate monobasic was added to neutralize, 727 parts of methyl isobutyl ketone was added, washing was repeated 3 times with 182 parts by mass of water, dried under heating under reduced pressure, and naphthol resin ( a-3) 350 mass parts was obtained. The hydroxyl group equivalent of the obtained naphthol resin (a-3) was 148 g / equivalent.
The epoxidation step was carried out in the same manner as in Example 1 to obtain 204 parts by mass of the target epoxy resin (A-3). The obtained epoxy resin (A-3) has an epoxy equivalent of 230 g / equivalent and a softening point of 112 ° C., and a GPC chart is shown in FIG. From the GPC chart, the content of the trimer (a1) is 16.8%, the content of the dimer (a2) is 3.7%, the content of the calixarene compound (a3) is 13.4%, and the high molecular weight The content rate of body (a4) was 66.1%.

Production Example 4 Production of Epoxy Resin (A-4) Epoxy resin in the same manner as in Example 3, except that β-naphthol was 144 parts (1.00 mol) and α-naphthol was 144 parts (1.00 mol). (A-4) 197 parts by mass were obtained. The obtained epoxy resin (A-4) has an epoxy equivalent of 228 g / equivalent and a softening point of 103 ° C., FIG. 6 shows a GPC chart, FIG. 7 shows an NMR chart, and FIG. 8 shows a MASS chart. From the GPC chart, the content of the trimer (a1) is 23.9%, the content of the dimer (a2) is 6.5%, the content of the calixarene compound (a3) is 5.5%, and the high molecular weight The content rate of a body (a4) was 64.1%.

Production Example 5 Production of Phenol Resin (B-1) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 505 parts by mass of α-naphthol (3.50 mol), 158 parts by mass of water Then, 5 parts by mass of oxalic acid was charged and stirred while raising the temperature from room temperature to 100 ° C. in 45 minutes. Subsequently, 177 parts by mass (2.45 mol) of a 42 mass% formalin aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated to 180 ° C. in 3 hours. After completion of the reaction, water remaining in the reaction system was removed under reduced pressure by heating to obtain 498 parts by mass of phenol resin (B-1). The softening point of the obtained phenol resin (B-1) was 133 ° C. (B & R method), and the hydroxyl group equivalent was 154 g / equivalent. The GPC chart of the obtained phenol resin (B-1) is shown in FIG. The area ratio in the GPC measurement of the α-naphthol monomer in the phenol resin composition (B-1) is 3.0%, and n in the general formula (i) (component in which R ¹ and R ² are hydrogen atoms) The average is 3.9, and the total area ratio in the GPC measurement of the binuclear body and the trinuclear body in the phenol resin composition (B-1) (in the general formula (i), R ¹ and R ² are hydrogen The sum of n = 1 and n = 2 in the case of atoms was 27.0%.

Production Example 6 Production of Phenolic Resin (B-2) α-Naphthol 505 parts by mass (3.50 mol), softening point 75 ° C. to a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer (B & R method) 21 parts of cresol novolak resin (number of moles of cresol skeleton: 0.18 mol), 158 parts by mass of water and 5 parts by mass of oxalic acid were charged and stirred while raising the temperature from room temperature to 100 ° C. in 45 minutes. Subsequently, 186 parts by mass (2.57 mol) of a 42 mass% formalin aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated to 180 ° C. in 3 hours. After completion of the reaction, a portion of free α-naphthol was removed by blowing steam under heating and decompression to obtain 505 parts by mass of a phenol resin (B-2). The obtained phenol resin (B-2) had a softening point of 137 ° C. (B & R method) and a hydroxyl group equivalent of 155 g / equivalent. The GPC chart of the obtained phenol resin (B-2) is shown in FIG. The area ratio in the GPC measurement of the α-naphthol monomer in the phenol resin (B-2) is 1.5%, and the average of n in the general formula (i) (the component in which R ¹ and R ² are hydrogen atoms) is 4.0, and the total area ratio in GPC measurement of the dinuclear body and the trinuclear body in the phenol resin composition (B-2) (in the general formula (i), R ¹ and R ² are hydrogen atoms) In this case, the sum of n = 1 body and n = 2 body) was 27.5%.

Production Example 7 Production of Phenol Resin (B-3) As raw material components, 505 parts by mass of α-naphthol (3.50 mol), 21 parts by mass of cresol novolac resin having a softening point of 75 ° C. (B & R method) (number of moles of cresol skeleton) : 0.18 mol), 521 parts by mass of a phenol resin (B-3) was obtained in the same manner as in Example 1 except that the amount was changed to 186 parts by mass (2.57 mol) of a 42% by mass formalin aqueous solution. The resulting phenolic resin (B-3) had a softening point of 129 ° C. (B & R method) and a hydroxyl group equivalent of 152 g / equivalent. FIG. 11 shows a GPC chart of the obtained phenol resin (B-3), FIG. 12 shows a ¹³ C-NMR chart, and FIG. 13 shows a spectrum of FD-MS. The area ratio in GPC measurement of the α-naphthol monomer in the phenol resin (B-3) is 3.8%, and the average of n in the general formula (i) (the component in which R ¹ and R ² are hydrogen atoms) is 4.0, and the total area ratio in the GPC measurement of the dinuclear body and the trinuclear body in the phenol resin composition (B-3) (in the general formula (i), R ¹ and R ² are hydrogen atoms) In this case, the sum of n = 1 body and n = 2 body) was 26.4%. The ratio of moles of phenol skeleton per mole of naphthol skeleton was 0.05.

Comparative Production Example 1 Production of phenolic resin (B′-1) α-naphthol 505 parts by mass (3.50 mol), softening point in a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer Charged 21 parts of cresol novolak resin at 75 ° C. (B & R method) (number of moles of cresol skeleton: 0.18 mol), 158 parts by mass of water and 5 parts by mass of oxalic acid, and stirred while raising the temperature from room temperature to 100 ° C. in 45 minutes. did. Then, 146 mass parts (2.02 mol) of 42 mass% formalin aqueous solution was dripped over 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated to 180 ° C. in 3 hours. After completion of the reaction, water remaining in the reaction system was removed under reduced pressure by heating to obtain 505 parts by mass of phenol resin (B′-1). The obtained phenol resin (B′-1) had a softening point of 95 ° C. (B & R method) and a hydroxyl group equivalent of 151 g / equivalent. FIG. 14 shows a GPC chart of the obtained phenol resin (B′-1). The area ratio in the GPC measurement of the α-naphthol monomer in the phenol resin (B′-1) is 10.2%, and the average of n in the general formula (i) (the component in which R ¹ and R ² are hydrogen atoms) Is 2.3, and the total area ratio in the GPC measurement of the binuclear body and the trinuclear body in the phenol resin composition (B′-1) (in the general formula (i), R ¹ and R ² are hydrogen atoms. In this case, the sum of n = 1 and n = 2) was 46.0%. The ratio of the number of moles of phenol skeleton per mole of naphthol skeleton was 0.05.

Comparative Production Example 2 Production of Phenolic Resin (B′-2) α-Naphthol 505 parts by mass (3.50 mol), water 158 in a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer Then, 5 parts by mass of oxalic acid and 5 parts by mass of oxalic acid were charged and stirred while raising the temperature from room temperature to 100 ° C. in 45 minutes. Subsequently, 186 parts by mass (2.57 mol) of a 42 mass% formalin aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated up to 180 ° C. in 3 hours. After completion of the reaction, the temperature was raised to 200 ° C., and steam was blown under reduced pressure to remove free α-naphthol to obtain 475 parts by mass of a phenol resin (B′-2). The obtained phenol resin (B′-2) had a softening point of 142 ° C. (B & R method) and a hydroxyl group equivalent of 157 g / equivalent. A GPC chart of the obtained phenol resin (B′-2) is shown in FIG. The area ratio in the GPC measurement of the α-naphthol monomer in the phenol resin (B′-2) is 0%, and the average of n in the general formula (i) (the component in which R1 and R2 are hydrogen atoms) is 4.0. And the total area ratio in the GPC measurement of the binuclear body and trinuclear body in the phenol resin (B′-2) (n = in the case where R ¹ and R ² are hydrogen atoms in the general formula (i)) The sum of 1 body and n = 2 bodies) was 27.4%.

Examples 1 to 10 and Comparative Examples 1 to 3
According to the composition described in Table 1 or 2 below, the above-mentioned (A-1) to (A-4) or “N-770” (phenol novolac type epoxy resin, epoxy equivalent 183 g / equivalent) made by DIC as an epoxy resin, The phenol resins (B-1) to (B-3), (B′-1) or (B′-2) are blended as curing agents, and 2-ethyl-4-methylimidazole (2E4MZ) is blended as a curing accelerator. And finally, methyl ethyl ketone was blended and adjusted so that the nonvolatile content (NV) of each composition was 58 mass%. Subsequently, it was cured under the following conditions to produce test pieces, and various performances were evaluated by the following methods. The results are shown in Table 1 or 2.

<Test specimen preparation 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

<Heat resistance test>
The glass transition temperature of the test piece is measured by the DMA method. Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min), the elastic modulus change is maximized (tan δ change rate is the highest). The (large) temperature was evaluated as the glass transition temperature. Temperature rising speed 3 ℃ / min

<Heat resistance change after thermal history (ΔTg): DMA (Tg difference between 1st run and 2nd run)>
The glass transition temperature of the test piece was measured under the following temperature conditions using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min). The temperature (Tg) at which the change in elastic modulus was maximized (the tan δ change rate was the largest) was measured twice.
Temperature condition 1st run: temperature increase from 35 ° C. to 275 ° C. at 3 ° C./min 2nd run: temperature difference from 35 ° C. to 330 ° C. at a temperature increase of 3 ° C./min was evaluated as ΔTg.

<Coefficient of thermal expansion>
A test piece was cut into a size of 5 mm × 5 mm × 0.8 mm, and thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: SS-6100 manufactured by Seiko Instruments Inc.).
Measurement conditions Measurement weight: 88.8mN
Temperature increase rate: 2 times at 10 ° C / minute Measurement temperature range: -50 ° C to 300 ° C
The measurement under the above conditions was carried out twice for the same sample, and the average linear expansion coefficient in the temperature range of 40 ° C. to 60 ° C. in the second measurement was evaluated as the thermal expansion coefficient.

Claims (8)

A curable resin composition containing an epoxy resin (A) and a phenol resin (B), wherein the epoxy resin (A) is
The following structural formula (1)

(In the formula, 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 G represents a glycidyl group.)
A trimer (a1) represented by:
The following structural formula (2)

(In the formula, 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 G represents a glycidyl group.)
And the dimer (a2) represented by the formula (2) as an essential component, and the phenol resin (B):
The following general formula (i)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an alkoxy group, and n is a repeating unit and is an integer of 1 or more.)
A naphthol novolac resin (b1) represented by:
The following general formula (ii)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an alkoxy group.)
And a compound (b2) represented by formula (b2) as an essential component. The epoxy resin (A) is an epoxy resin obtained by polyglycidyl etherification of a polycondensate of an α-naphthol compound, a β-naphthol compound, and formaldehyde, and the trimer (a1) has an area ratio of 15 in GPC measurement. 2. The curable resin composition according to claim 1, wherein the curable resin composition contains the dimer (a2) at a ratio of 1 to 25% in terms of an area ratio in GPC measurement. In addition to the trimer (a1) and the dimer (a2), the epoxy resin (A) is further represented by the following structural formula (3)

(In the formula, 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, G represents a glycidyl group, and n represents a repeating group. It is a unit and is an integer of 2 to 10.)
The curable resin composition according to claim 1, comprising a calixarene compound (a3) represented by: The curable resin composition according to claim 3, wherein the epoxy resin (A) contains the calixarene type compound (a3) at a ratio of 1 to 40% in terms of area ratio in GPC measurement. The phenol resin (B) contains the n = 1 body and the n = 2 body in the general formula (i) at a ratio such that the sum thereof is in the range of 10 to 35% in area ratio in GPC measurement, The average of n in the general formula (i) is in the range of 3.0 to 7.0, and the compound (b2) is contained at a ratio of 1 to 6% in terms of area ratio in GPC measurement. Item 2. A curable resin composition according to Item 1. The curable resin composition according to claim 1, wherein the phenol resin (B) further contains a phenol novolak or an alkylphenol novolak component (b3) in addition to the naphthol novolak resin (b1) and the compound (b2). Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of Claims 1-6. A printed wiring obtained by impregnating a reinforcing base material with a varnish composition further blended with the curable composition according to any one of claims 1 to 6 and overlaying a copper foil thereon and heat-pressing the varnish composition. substrate.

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