JP7192485B2 - Xanthene type resin, curable resin composition and cured product thereof - Google Patents

Description

The present invention provides a xanthene-type phenolic resin, a xanthene-type epoxy resin, and a xanthene-type epoxy resin that have good fluidity during heat processing and excellent low-shrinkage properties during heat-curing and can be suitably used for semiconductor encapsulating materials and the like. The present invention relates to a curable resin composition containing a resin and a cured product thereof.

Curable resin compositions using epoxy resins and various curing agents are used for adhesives, molding materials, paints, photoresist materials, color developer materials, etc. In addition, the cured products obtained have excellent heat resistance and moisture resistance. It is widely used in the electrical and electronic fields such as semiconductor sealing materials and insulating materials for printed wiring boards due to its excellent properties.

Among these various applications, there is a strong demand for thinning and weight reduction in the electrical and electronic fields, and wafer level packaging technology is one of the mounting techniques that meet these demands. Wafer-level packaging technology is a mounting technology that manufactures semiconductor packages by performing resin sealing, rewiring, and electrode formation on a wafer, and then dividing the wafer into individual pieces by dicing. Since the encapsulation resin is used for collective encapsulation, warpage occurs due to contraction during curing of the resin and a difference in shrinkage caused by the coefficient of linear expansion of the chip and the coefficient of linear expansion of the encapsulation resin. Since this warpage significantly lowers the reliability of the package, the encapsulation resin is required to have a low viscosity and low shrinkage in order to suppress the warp.

An epoxy resin having an allyl group as a substituent on an aromatic ring of a bisphenol skeleton has been provided as an epoxy resin that can be suitably used as a semiconductor sealing material (see, for example, Patent Document 1). Alternatively, it is also known that a naphthylene ether skeleton-containing epoxy resin, which may have a substituent on the aromatic ring, is suitably used as a semiconductor sealing material (see, for example, Patent Document 2).

Phenolic resins are also used as curing agents for epoxy resins, and as phenolic resins that can be suitably used as epoxy resin curing agents for electronic materials, particularly laminates with excellent moisture resistance and solder resistance. , for example, a phenolic novolac resin containing 25% by mass or more of a trifunctional compound, and a resin characterized by having a substituent on at least one aromatic ring of phenol constituting the resin is provided ( For example, see Patent Document 3).

As described above, by using an epoxy resin or phenolic resin having a substituent on the aromatic ring as a resin component of a curable resin composition, the composition can be improved more than when using a general bisphenol-type epoxy resin or phenolic novolac resin. Although a certain effect can be obtained in the fluidity of the product and the dimensional stability at the time of curing, it cannot satisfy the mold shrinkage rate and high fluidity at the time of heat curing of the resin composition required in recent years at a high level. Further improvements are required.

JP 2015-000952 A JP 2016-89096 A JP-A-7-10967

Therefore, the problem to be solved by the present invention is to provide a xanthene-type phenol resin, a xanthene-type epoxy resin, and a curability that are excellent in the balance between the flowability of a composition containing a phenol resin or an epoxy resin during heat curing and the molding shrinkage rate. An object of the present invention is to provide a composition and a cured product thereof.

In order to solve the above problems, the present inventors have made intensive studies and found that a phenolic resin having a xanthene skeleton having a substituent on an aromatic ring, or an epoxy resin obtained by glycidylating the same has a The inventors have found that the fluidity and mold shrinkage are excellent, and have completed the present invention.

That is, the present invention has the following general formula (1)

〔式中、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ独立して炭素原子数４～８のアルキル基又はアラルキル基であり、ｌは０，１，２の何れかであり、ｍは０又は１であり、ｎは０又は１であり（但し、ｌ＝ｍ＝ｎ＝０の場合を除く）、Ｒ^４、Ｒ^５はそれぞれ独立に水素原子、炭素原子数４～８のアルキル基又はアラルキル基であり、
Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９はそれぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ^６、Ｒ^７、のうちいずれかはアルキル基又はアリール基であり、Ｒ^８、Ｒ^９のうちいずれかはアルキル基又はアリール基であり、
ｐ、ｑ、ｒはそれぞれ独立に０又は１であり（但し、ｐ＝ｑ＝ｒ＝０の場合を除く）、
ｓは繰り返し数を示し、０～１０の整数である。〕
で表されることを特徴とするキサンテン型フェノール樹脂、およびこれ含む硬化性樹脂組成物とその硬化物を提供するものである。

[In the formula, R ¹ , R ² and R ³ are each independently an alkyl group or an aralkyl group having 4 to 8 carbon atoms, l is any one of 0, 1 or 2, m is 0 or 1 and n is 0 or 1 (except when l = m = n = 0), R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms, or an aralkyl group and
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, any one of ^{R 6} and R ⁷ is an alkyl group or an aryl group, any of ⁹ is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
s indicates the number of repetitions and is an integer of 0-10. ]
To provide a xanthene-type phenol resin characterized by being represented by, a curable resin composition containing the same, and a cured product thereof.

Furthermore, the present invention provides the following general formula (2)

〔式中、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ独立して炭素原子数４～８のアルキル基又はアラルキル基であり、ｌは０，１，２の何れかであり、ｍは０又は１であり、ｎは０又は１であり（但し、ｌ＝ｍ＝ｎ＝０の場合を除く）、Ｒ^４、Ｒ^５はそれぞれ独立に水素原子、炭素原子数４～８のアルキル基又はアラルキル基であり、
Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９はそれぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ^６、Ｒ^７、のうちいずれかはアルキル基又はアリール基であり、Ｒ^８、Ｒ^９のうちいずれかはアルキル基又はアリール基であり、
ｐ、ｑ、ｒはそれぞれ独立に０又は１であり（但し、ｐ＝ｑ＝ｒ＝０の場合を除く）、
Ｇはグリシジル基であり、ｓは繰り返し数を示し、０～１０の整数である。〕
で表されることを特徴とするキサンテン型エポキシ樹脂、およびこれ含む硬化性樹脂組成物とその硬化物を提供するものである。

[In the formula, R ¹ , R ² and R ³ are each independently an alkyl group or an aralkyl group having 4 to 8 carbon atoms, l is any one of 0, 1 or 2, m is 0 or 1 and n is 0 or 1 (except when l = m = n = 0), R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms, or an aralkyl group and
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, any one of ^{R 6} and R ⁷ is an alkyl group or an aryl group, any of ⁹ is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
G is a glycidyl group, s is an integer of 0 to 10 and represents the number of repetitions. ]
To provide a xanthene-type epoxy resin characterized by being represented by, a curable resin composition containing the same, and a cured product thereof.

According to the present invention, xanthene-type phenolic resins, xanthene-type epoxy resins, xanthene-type epoxy resins, which are excellent in the balance of fluidity, molding shrinkage, and elastic modulus during heat curing of the resin composition, and which can be suitably used for semiconductor encapsulation materials, etc. It is possible to provide a curable resin composition, a cured product having the above properties, a semiconductor encapsulating material, and the like.

1 is a ¹³ C-NMR chart of the phenolic resin (1) synthesized in Example 1. FIG. 2 is an MS chart of the phenolic resin (1) synthesized in Example 1. FIG. 3 is a GPC chart of the phenolic resin (1) synthesized in Example 1. FIG. 4 is a ¹³ C-NMR chart of the epoxy resin (2) synthesized in Example 2. FIG. 5 is an MS chart of the epoxy resin (2) synthesized in Example 2. FIG. 6 is a GPC chart of the epoxy resin (2) synthesized in Example 2. FIG.

<Phenolic resin>
The present invention will be described in detail below.
The phenol resin of the present invention has the following general formula (1)

〔式中、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ独立して炭素原子数４～８のアルキル基又はアラルキル基であり、ｌは０，１，２の何れかであり、ｍは０又は１であり、ｎは０又は１であり（但し、ｌ＝ｍ＝ｎ＝０の場合を除く）、Ｒ^４、Ｒ^５はそれぞれ独立に水素原子、炭素原子数４～８のアルキル基又はアラルキル基であり、
Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９はそれぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ^６、Ｒ^７、のうちいずれかはアルキル基又はアリール基であり、Ｒ^８、Ｒ^９のうちいずれかはアルキル基又はアリール基であり、
ｐ、ｑ、ｒはそれぞれ独立に０又は１であり（但し、ｐ＝ｑ＝ｒ＝０の場合を除く）、
ｓは繰り返し数を示し、０～１０の整数である。〕
で表されることを特徴とする。

[In the formula, R ¹ , R ² and R ³ are each independently an alkyl group or an aralkyl group having 4 to 8 carbon atoms, l is any one of 0, 1 or 2, m is 0 or 1 and n is 0 or 1 (except when l = m = n = 0), R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms, or an aralkyl group and
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, any one of ^{R 6} and R ⁷ is an alkyl group or an aryl group, any of ⁹ is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
s indicates the number of repetitions and is an integer of 0-10. ]
It is characterized by being represented by

The phenolic resin of the present invention contains at least R ¹ , R ² and R ³ in the general formula (1), that is, an alkyl group or an aralkyl group having 4 to 8 carbon atoms as a substituent on the aromatic ring. have one. By having such relatively bulky substituents, it is believed that the crosslink density during the curing reaction is appropriately adjusted, and the molding shrinkage during heat curing becomes low. As the alkyl group, an alkyl group having a branched structure such as a t-butyl group, a t-amyl group and a t-octyl group is preferable, and a t-butyl group or a t-octyl group is particularly preferable. The aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, particularly preferably a benzyl group.

Further, the phenolic resin of the present invention is a mixture of a plurality of compounds having different s in the general formula (1) and a novolac-type phenolic resin that does not form a xanthene skeleton. is preferably in the range of 50 to 75% in terms of area ratio in GPC measurement, from the viewpoint of better fluidity of the curable composition.

The GPC measurement in the present invention is performed under the following conditions, and the area % can be calculated from the obtained chart.

<GPC measurement conditions>
Measuring device: "HLC-8320 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
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" 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 the "GPC Workstation EcoSEC-WorkStation".
(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: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)

R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (1) are each independently a hydrogen atom, an alkyl group or an aryl group, particularly a hydrogen atom or a An alkyl group or an aryl group having 6 to 14 carbon atoms is preferable from the viewpoint of facilitating compatibility between the fluidity of the curable resin composition and the suppression of heat shrinkage during curing, and the production method described later. From the viewpoint of easy raw material availability when producing this resin, it is preferable that R ⁶ and R ⁸ are benzene rings.

Furthermore, the hydroxyl equivalent weight of the phenolic resin of the present invention is preferably in the range of 150 to 300 g/eq from the viewpoint of good fluidity of the curable resin composition and good curability during heat curing.

<Epoxy resin>
The epoxy resin of the present invention has the following general formula (2)

〔式中、Ｒ^１、Ｒ^２、Ｒ^３はそれぞれ独立して炭素原子数４～８のアルキル基又はアラルキル基であり、ｌは０，１，２の何れかであり、ｍは０又は１であり、ｎは０又は１であり（但し、ｌ＝ｍ＝ｎ＝０の場合を除く）、Ｒ^４、Ｒ^５はそれぞれ独立に水素原子、炭素原子数４～８のアルキル基又はアラルキル基であり、
Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９はそれぞれ独立に、水素原子、アルキル基又はアリール基であり、Ｒ^６、Ｒ^７、のうちいずれかはアルキル基又はアリール基であり、Ｒ^８、Ｒ^９のうちいずれかはアルキル基又はアリール基であり、
ｐ、ｑ、ｒはそれぞれ独立に０又は１であり（但し、ｐ＝ｑ＝ｒ＝０の場合を除く）、
Ｇはグリシジル基であり、ｓは繰り返し数を示し、０～１０の整数である。〕
で表されることを特徴とする。

[In the formula, R ¹ , R ² and R ³ are each independently an alkyl group or an aralkyl group having 4 to 8 carbon atoms, l is any one of 0, 1 or 2, m is 0 or 1 and n is 0 or 1 (except when l = m = n = 0), R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms, or an aralkyl group and
R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, any one of ^{R 6} and R ⁷ is an alkyl group or an aryl group, any of ⁹ is an alkyl group or an aryl group,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
G is a glycidyl group, s is an integer of 0 to 10 and represents the number of repetitions. ]
It is characterized by being represented by

The epoxy resin of the present invention contains at least R ¹ , R ² and R ³ in the general formula (2), that is, an alkyl group or an aralkyl group having 4 to 8 carbon atoms as a substituent on the aromatic ring. have one. By having such relatively bulky substituents, it is believed that the crosslink density during the curing reaction is appropriately adjusted, and the molding shrinkage during heat curing becomes low. As the alkyl group, an alkyl group having a branched structure such as a t-butyl group, a t-amyl group and a t-octyl group is preferable, and a t-butyl group or a t-octyl group is particularly preferable. The aralkyl group is preferably an aralkyl group having 7 to 15 carbon atoms, particularly preferably a benzyl group.

In addition, the epoxy resin of the present invention is a mixture of a plurality of compounds having different s in the general formula (2) and a novolak-type epoxy resin that does not form a xanthene skeleton. is preferably in the range of 30 to 50% in terms of area ratio in GPC measurement, from the viewpoint of better fluidity of the curable composition.

The GPC measurement in the present invention is performed under the following conditions, and the area % can be calculated from the obtained chart.

<GPC measurement conditions>
Measuring device: "HLC-8320 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
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" 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 the "GPC Workstation EcoSEC-WorkStation".
(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: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl)

R ⁶ , R ⁷ , R ⁸ and R ⁹ in the general formula (2) are each independently a hydrogen atom, an alkyl group or an aryl group, particularly a hydrogen atom or a An alkyl group or an aryl group having 6 to 14 carbon atoms is preferable from the viewpoint of facilitating compatibility between the fluidity of the curable resin composition and the suppression of heat shrinkage during curing, and the production method described later. From the viewpoint of easy raw material availability when producing this resin, it is preferable that R ⁶ and R ⁸ are benzene rings.

Furthermore, the epoxy equivalent of the epoxy resin of the present invention is preferably in the range of 300 to 500 g/eq from the viewpoint of the fluidity of the curable resin composition and the curability during heat curing. The melt viscosity is preferably in the range of 0.1 to 40 dPa·s at 150°C.

The phenol resin or epoxy resin of the present invention is, for example, represented by the following structural formula.

(In the formula, OX represents OH or glycidyl ether.)

<Method for producing phenolic resin>
The phenolic resin of the present invention uses dihydroxybenzene (I) having an alkyl group having 4 to 8 carbon atoms on the aromatic ring and aldehydes (II) having an alkyl group or an aryl group to produce intramolecular A method using a ring closure reaction is preferred.

Examples of the dihydroxybenzene (I) include monoalkyldihydroxybenzenes such as n-butylhydroquinone, n-butylresorcinol, n-butylcatechol, sec-butylhydroquinone, sec-butylresorcinol, sec-butylcatechol and t-butyl. hydroquinone, t-butylresorcinol, t-butylcatechol, n-hexylhydroquinone, n-hexylresorcinol, 4-octylcatechol, etc. Examples of dialkyldihydroxybenzenes include 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroquinone, etc., may be used alone or in combination of two or more. Among these, from the viewpoint of the heat shrinkage rate of the curable resin composition using the obtained phenol resin, it is preferable to have an alkyl group with a bulkier structure. It is most preferable to use t-butylcatechol and 3,5-di-t-butylcatechol from the viewpoint of the properties of the composition when cured.

Furthermore, you may use a monohydroxy aromatic compound together. Of these, monocyclic monohydroxyaromatic compounds include alkylphenols such as phenol, o-cresol, p-cresol, m-cresol, butylphenol, xylenol, nonylphenol and octylphenol, phenylphenol, bisphenol A, bisphenol F and bisphenol S. , amylphenol, pyrogallol, allylphenol, bisphenol fluorenes, and polycyclic monohydroxyaromatic compounds such as 1-naphthol and 2-naphthol, which are commonly used in the synthesis of phenolic resins. , may be used in combination of two or more.

Examples of the aldehydes (II) having an alkyl group or an aryl group include formaldehyde, paraldehyde, benzaldehyde, anisaldehyde, naphthaldehyde, anthraldehyde, and the like, and benzaldehyde can be used from the viewpoint of easy xanthene conversion. preferable. When benzaldehyde is used as a starting material, aralkylation occurs, so the phenolic resin of the present invention can be obtained even when unsubstituted dihydroxybenzene is used as a starting material.

These phenols and aldehydes are preferably reacted in the presence of a basic catalyst in an amount of 0.3 to 0.9 mol of aldehydes per 1 mol of phenols. More preferably, 0.4 to 0.8 mol is reacted. When the amount of aldehydes is less than 0.3 mol, a novolac resin is formed, but the content of the xanthene derivative is low and the amount of unreacted phenols increases, which tends to reduce the amount of resin formed. If the amount of aldehydes exceeds 0.9 mol, it is advantageous in terms of the amount of resin produced, but gelation tends to occur in the reaction system, and it tends to be extremely difficult to control the reaction.

Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates and alkali metal hydroxides. In particular, alkali metal hydroxides are preferred from the viewpoint of excellent catalytic activity in the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. When used, these basic catalysts may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or may be used in the form of a solid.

The reaction may be carried out in an organic solvent, and usable organic solvents include, for example, methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is not particularly limited, and from the viewpoint of work efficiency, for example, it should be in the range of 10 to 300 parts by mass per 100 parts by mass of o-allylphenol as a raw material component. is preferred.

After completion of the reaction, it is preferable to neutralize or wash with water until the pH value of the reaction mixture reaches 6-8. Neutralization treatment and washing treatment may be carried out according to conventional methods, and for example, an acidic substance such as monosodium phosphate can be used as a neutralizing agent. After the neutralization or washing with water, the organic solvent is distilled off under heating under reduced pressure to obtain the desired phenol resin.

<Method for producing epoxy resin>
The epoxy resin of the present invention can be obtained by epoxidizing the xanthene-type phenolic resin obtained by the method described above.

Further, other diphenols may be used in combination as long as the effects of the present invention are not impaired.

The method for producing the epoxy resin of the present invention is a method for producing an epoxy resin in which the xanthene-type phenolic resin of the present invention is reacted with epihalohydrin to epoxidize it, as described above. can be done.

For example, 1 to 10 mol of epihalohydrin is added to 1 mol of hydroxyl groups contained in the xanthene-type phenolic resin, and 0.9 to 2.0 mol of a basic catalyst is added at once to 1 mol of hydroxyl groups of the raw material. Alternatively, a method of reacting at a temperature of 20 to 120° C. for 0.5 to 10 hours while gradually adding them may be used. This basic catalyst may be solid or an aqueous solution thereof may be used. 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. A method may also be used in which the water is removed by liquid separation and the epihalohydrin is continuously returned to the reaction mixture.

When carrying out industrial production, in the first batch of epoxy resin production, all the epihalohydrins used for charging are new, but from the next batch onwards, the epihalohydrins recovered from the crude reaction product and the epihalohydrins consumed in the reaction are used. It is preferable to use new epihalohydrins corresponding to the amount that disappears as soon as possible. At this time, it may contain impurities such as glycidol that are induced by the reaction of epichlorohydrin with water, an organic solvent, or the like. The epihalohydrin used at this time is not particularly limited, but examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like. Among these, epichlorohydrin is preferable because it is easily available industrially.

Moreover, the basic catalyst specifically includes an alkaline earth metal hydroxide, an alkali metal carbonate, an alkali metal hydroxide, and the like. In particular, alkali metal hydroxides are preferred from the viewpoint of excellent catalytic activity in the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. When used, these basic catalysts may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or may be used in the form of a solid. Moreover, by using an organic solvent together, the reaction rate in the synthesis of the epoxy resin can be increased. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol; Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide. These organic solvents may be used alone, or two or more of them may be used in combination to adjust the polarity.

Subsequently, after the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent 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 dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, etc., and alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc. is added. Further reaction can be carried out by adding an aqueous solution of the substance. 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 a phase transfer catalyst is used, the amount used is preferably in the range of 0.1% by mass to 3.0% by mass relative to the epoxy resin used. After completion of the reaction, the produced salt is removed by filtration, washing with water, or the like, and a solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure to obtain a highly pure epoxy resin.

In particular, in order to obtain the epoxy resin of the present invention, the desired epoxy resin can be efficiently obtained by adjusting the water concentration in the solvent to 5 to 25% when the xanthene-type phenol resin and epichlorohydrin are reacted. can.

<Curable resin composition containing xanthene-type phenolic resin>
The phenolic resin of the present invention can be made into a curable resin composition by using together with another compound having a functional group that reacts with a hydroxyl group, that is, a curing agent (X). The curable resin composition can be suitably used for various electrical and electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor sealing materials.

Examples of the curing agent (X) include melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resol resins, epoxy resins, and epoxy compounds substituted with at least one group selected from methylol groups, alkoxymethyl groups, and acyloxymethyl groups. Examples include resins, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, acid anhydrides, oxazoline compounds, and the like.

Examples of the melamine compound include hexamethylolmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylolmelamine are methoxymethylated, and methylols of hexamethoxyethylmelamine, hexaacyloxymethylmelamine, and hexamethylolmelamine. Examples include compounds in which 1 to 6 groups are acyloxymethylated.

The guanamine compounds include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, tetramethoxymethylbenzoguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, tetramethoxyethylguanamine, tetraacyloxyguanamine, tetra Examples include compounds in which 1 to 4 methylol groups of methylolguanamine are acyloxymethylated.

The glycoluril compounds include, for example, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis ( hydroxymethyl)glycoluril and the like.

Examples of the urea compound include 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1,1,3,3-tetrakis(methoxymethyl)urea. be done.

The resol resin is, for example, phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, phenolic hydroxyl group-containing compounds such as dihydroxynaphthalene, and aldehyde compounds. Examples include polymers obtained by reacting under catalytic conditions.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, diglycidyloxynaphthalene, naphthol aralkyl type epoxy resin, naphthol- Phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl modified novolak type epoxy resin, 1,1-bis(2,7-diglycidyl oxy-1-naphthyl)alkanes, naphthylene ether type epoxy resins, triphenylmethane type epoxy resins, phosphorus atom-containing epoxy resins, polyglycidyl ethers of co-condensates of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, etc. , or the xanthene-type epoxy resin of the present invention. Among these epoxy resins, tetramethylbiphenol-type epoxy resin, biphenylaralkyl-type epoxy resin, polyhydroxynaphthalene-type epoxy resin, and novolac-type epoxy resin can be used in view of obtaining cured products having particularly excellent flame retardancy. A dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties can be obtained.

Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, and the like.

Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.

Examples of compounds containing double bonds such as alkenyl ether groups include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, and tetramethylene glycol divinyl ether. , neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether etc.

The acid anhydrides are, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4 Aromatic acid anhydrides such as '-(isopropylidene)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride , methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and trialkyltetrahydrophthalic anhydride.

Among these, the epoxy resin is particularly preferable because it provides a curable composition having excellent curability and heat resistance in the cured product.

Furthermore, when the epoxy resin is used, an epoxy resin curing agent may be blended.

Examples of epoxy resin curing agents that can be used here include various known epoxy resin curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.

Specifically, amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives and the like. Amide compounds include dicyandiamide. , a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine. Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydro Examples include phthalic anhydride and the like. Phenolic compounds include phenol novolak resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, triphenylolmethane resin, Tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyphenolic hydroxyl group-containing compound with phenolic nucleus linked by bismethylene group), biphenyl Modified naphthol resins (polyhydric naphthol compounds with phenolic nuclei linked by bismethylene groups), aminotriazine-modified phenolic resins (compounds containing polyhydric phenolic hydroxyl groups with phenolic nuclei linked with melamine, benzoguanamine, etc.) and aromatic rings containing alkoxy groups Examples include polyphenolic hydroxyl group-containing compounds such as modified novolak resins (polyphenolic hydroxyl group-containing compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

<Curable resin composition containing xanthene-type epoxy resin>
The xanthene-type epoxy resin of the present invention can be made into a curable resin composition by using various curing agents (Y) having a group reactive with an epoxy group. The curable resin composition can be suitably used for various electrical and electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor sealing materials.

Examples of the curing agent (Y) that can be used here include various known epoxy resin curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.

Specifically, amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives and the like. Amide compounds include dicyandiamide. , a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine. Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydro Examples include phthalic anhydride and the like. Phenolic compounds include phenol novolak resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, triphenylolmethane resin, Tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyphenolic hydroxyl group-containing compound with phenolic nucleus linked by bismethylene group), biphenyl Modified naphthol resins (polyhydric naphthol compounds with phenolic nuclei linked by bismethylene groups), aminotriazine-modified phenolic resins (compounds containing polyhydric phenolic hydroxyl groups with phenolic nuclei linked with melamine, benzoguanamine, etc.) and aromatic rings containing alkoxy groups Examples include polyphenolic hydroxyl group-containing compounds such as modified novolak resins (polyphenolic hydroxyl group-containing compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde). Furthermore, the xanthene-type phenolic resin of the present invention may be used.

Furthermore, in the curable resin composition of the present invention, epoxy resins other than the epoxy resins defined above can be used in combination within a range that does not impair the effects of the present invention.

Examples of the other epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, biphenyl-type epoxy resin, tetramethylbiphenyl-type epoxy resin, polyhydroxynaphthalene-type epoxy resin, phenol novolak-type epoxy resin, and cresol novolak-type epoxy resin. Epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol co- Condensed novolac epoxy resins, naphthol-cresol cocondensed novolac epoxy resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resin-type epoxy resins, biphenyl-modified novolak-type epoxy resins, and the like. Among these epoxy resins, tetramethylbiphenol-type epoxy resin, biphenylaralkyl-type epoxy resin, polyhydroxynaphthalene-type epoxy resin, and novolac-type epoxy resin can be used in view of obtaining cured products having particularly excellent flame retardancy. A dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties can be obtained. In addition, when other epoxy resins are used in combination, the effect of the present invention is that the epoxy resin of the present invention is contained in an amount of 30 to 90 parts by mass with respect to the total of 100 parts by mass of the epoxy resin of the present invention and other epoxy resins. is preferable from the viewpoint of being able to express easily.

In the curable resin composition of the present invention, the blending amount of the epoxy resin and the curing agent (Y) should be the amount of the epoxy groups in the other epoxy resin used in combination with the epoxy resin, from the viewpoint of excellent curability. The ratio is preferably such that the total amount of active groups in the curing agent (Y) is 0.8 to 1.2 equivalents with respect to the total amount of 1 equivalent.

<Other ingredients>
In the present invention, other thermosetting resins may be used in combination with both the curable resin composition containing the phenol resin and the curable resin composition containing the epoxy resin.

Other thermosetting resins include, for example, cyanate ester resins, resins having a benzoxazine structure, maleimide compounds, active ester resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, and the like. . When other thermosetting resins are used in combination, the amount used is not particularly limited as long as it does not impair the effects of the present invention. Preferably.

Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, and phenylene ether type cyanate ester resin. , naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate Ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol cocondensed novolak type cyanate ester resins, naphthol-cresol cocondensed novolak type cyanate ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resins, biphenyl-modified novolac type cyanate ester resins, anthracene type cyanate ester resins, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Among these cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, and polyhydroxynaphthalene-type cyanate ester resins are particularly useful in terms of obtaining cured products with excellent heat resistance. , a naphthylene ether type cyanate ester resin, and a novolac type cyanate ester resin are preferably used, and a dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.

Resins having a benzoxazine structure are not particularly limited. d-type benzoxazine resin), reaction product of bisphenol A, formalin and aniline, reaction product of dihydroxydiphenyl ether, formalin and aniline, reaction product of diaminodiphenyl ether, formalin and phenol, dicyclopentadiene-phenol addition type resin and formalin and aniline, reaction products of phenolphthalein, formalin and aniline, and reaction products of diphenylsulfide, formalin and aniline. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the maleimide compound include various compounds represented by any one of the following structural formulas (i) to (iii).

（式中Ｒはｍ価の有機基であり、α及びβはそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基の何れかであり、ｓは１以上の整数である。）

(In the formula, R is an m-valent organic group, α and β are each a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and s is an integer of 1 or more.)

（式中Ｒは水素原子、アルキル基、アリール基、アラルキル基、ハロゲン原子、水酸基、アルコキシ基の何れかであり、ｓは１～３の整数、ｔは繰り返し単位の平均で０～１０である。）

(In the formula, R is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, s is an integer of 1 to 3, and t is an average repeating unit of 0 to 10. .)

（式中Ｒは水素原子、アルキル基、アリール基、アラルキル基、ハロゲン原子、水酸基、アルコキシ基の何れかであり、ｓは１～３の整数、ｔは繰り返し単位の平均で０～１０である。）これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。

(In the formula, R is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, s is an integer of 1 to 3, and t is an average repeating unit of 0 to 10. ) Each of these may be used alone, or two or more of them may be used in combination.

The active ester resin is not particularly limited, but generally contains an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and/or a naphthol compound is preferred. more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and halides thereof. Phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m - cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine , benzenetriol, and dicyclopentadiene-phenol addition type resins.

Specific active ester resins include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated products of phenol novolak, and active ester resins that are benzoylated products of phenol novolak. Ester resins and the like are preferred, and active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred in that they are excellent in improving peel strength. Active ester resins containing a dicyclopentadiene-phenol addition structure include, more specifically, compounds represented by the following general formula (iv).

However, in formula (iv), R is a phenyl group or a naphthyl group, u represents 0 or 1, and n is 0.05 to 2.5 on average for repeating units. From the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition and improving the heat resistance, R is preferably a naphthyl group, u is preferably 0, and n is preferably 0.25 to 1.5. .

Furthermore, various novolak resins, addition polymerization resins of alicyclic diene compounds such as dicyclopentadiene and phenolic compounds, modified novolac resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zyloc resins) ), naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, and various vinyl polymers may be used in combination.

More specifically, the various novolak resins are produced by reacting phenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, dihydroxynaphthalene, and other phenolic hydroxyl group-containing compounds with an aldehyde compound as an acid catalyst. Examples include polymers obtained by reacting under conditions.

The various vinyl polymers mentioned above include polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly( Examples thereof include homopolymers of vinyl compounds such as meth)acrylates and copolymers thereof.

When these other resins are used, the blending ratio can be arbitrarily set according to the application, but the fluidity as a composition that the present invention exerts and the molding shrinkage rate at the time of heat curing are more remarkably balanced. Therefore, it is preferable that the proportion of the other resin is 0.5 to 100 parts by mass with respect to 100 parts by mass of the phenol resin or epoxy resin of the present invention.

A curing accelerator may be used in combination with the curable resin composition of the present invention. Curing accelerators include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and boron trifluoride monoethylamine complex; thiodipropion organic acid compounds such as acids; benzoxazine compounds such as thiodiphenolbenzoxazine and sulfonylbenzoxazine; and sulfonyl compounds. Each of these may be used alone, or two or more of them may be used in combination. The amount of these catalysts added is preferably in the range of 0.001 to 15 parts by mass per 100 parts by mass of the curable resin composition.

Further, when the curable resin composition of the present invention is used in applications where high flame retardancy is required, a non-halogen flame retardant that does not substantially contain halogen atoms may be blended.

Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc., and their use is also subject to any restrictions. A single flame retardant may be used alone, or a plurality of flame retardants of the same type may be used, or flame retardants of different types may be used in combination.

Both inorganic and organic phosphorus flame retardants can be used. Examples of 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 phosphoramide. .

In addition, the red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis, etc. Examples of surface treatment methods include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and the like, and A method of coating with a mixture of a thermosetting resin such as a phenolic resin, (iii) a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. is coated with a thermosetting resin such as a phenolic resin. A method of double-coating with a resin and the like can be mentioned.

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

The amount of these phosphorus-based flame retardants to be blended is appropriately selected depending on the type of phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. and other fillers, additives, etc., in 100 parts by mass of the resin composition, when red phosphorus is used as a non-halogen flame retardant, blended in the range of 0.1 to 2.0 parts by mass When an organic phosphorus compound is used, it is preferably blended in the range of 0.1 parts by mass to 10.0 parts by mass, and blended in the range of 0.5 parts by mass to 6.0 parts by mass. is more preferable.

When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. may be used in combination with the phosphorus-based flame retardant. good.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, etc. Triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred.

Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, and (1) guanylmelamine sulfate, melem sulfate, and melam sulfate. (2) co-condensation products of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde; (2) mixtures of cocondensates and phenolic resins such as phenol-formaldehyde condensates;

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

The amount of the nitrogen-based flame retardant to be blended is appropriately selected depending on the type of nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. In 100 parts by mass of the resin composition containing all other fillers, additives, etc., it is preferably blended in the range of 0.05 to 10 parts by mass, and blended in the range of 0.1 part by mass to 5 parts by mass. is more preferable.

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

Any organic compound containing a silicon atom can be used as the silicone-based flame retardant without particular limitation, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicone flame retardant compounded is appropriately selected depending on the type of the silicone flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferable to mix 0.05 to 20 parts by mass in 100 parts by mass of the resin composition containing all 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 hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.

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

Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like can be mentioned.

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

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

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

Examples of the low-melting glass include Seapley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ -B ₂ O ₃ -PbO-MgO system, P-Sn-OF system, PbO-V ₂ O ₅ -TeO ₂ system, Al ₂ O ₃ -H ₂ O system, glassy compounds such as lead borosilicate system can be mentioned.

The amount of the inorganic flame retardant compounded is appropriately selected depending on the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. In 100 parts by mass of the resin composition containing all other fillers, additives, etc., it is preferably blended in the range of 0.05 parts by mass to 20 parts by mass, and the range of 0.5 parts by mass to 15 parts by mass. It is more preferable to blend with

The organometallic salt-based flame retardants include, for example, ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, and metal atoms and aromatic compounds or heterocyclic compounds in ionic bonds or coordination. Examples thereof include compounds in which positional bonds are formed.

The amount of the organometallic salt-based flame retardant to be blended is appropriately selected depending on the type of the organometallic salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferable to mix 0.005 parts by mass to 10 parts by mass with respect to 100 parts by mass of the resin composition in which the halogen-based flame retardant and other fillers and additives are all blended.

The curable resin composition of the present invention may optionally contain an inorganic filler. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the blending amount of the inorganic filler is particularly large, it is preferable to use fused silica. The fused silica may be crushed or spherical, but it is preferable to mainly use spherical fused silica in order to increase the blending amount of fused silica and suppress an increase in the melt viscosity of the molding material. Furthermore, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. Considering flame retardancy, the filling rate is preferably as high as possible, and is particularly preferably 20% by mass or more relative to the total mass of the curable resin composition. Moreover, when using for applications, such as an electroconductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

In addition, the curable resin composition of the present invention may optionally contain various compounding agents such as silane coupling agents, release agents, pigments and emulsifiers.

<Application of curable resin composition>
The curable resin composition of the present invention can be applied to semiconductor sealing materials, semiconductor devices, prepregs, printed circuit boards, build-up boards, build-up films, fiber-reinforced composite materials, fiber-reinforced resin moldings, conductive pastes, and the like. can be done.

1. Semiconductor encapsulating material As a method for obtaining a semiconductor encapsulating material from the curable resin composition of the present invention, the curable resin composition and compounding agents such as inorganic fillers are optionally extruded and kneaded. , a method of sufficiently melting and mixing using a roll or the like until uniform. At that time, fused silica is usually used as the inorganic filler, but when it is used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and nitride, which have higher thermal conductivity than fused silica, are used. It is preferable to use high filling of silicon or the like, or fused silica, crystalline silica, alumina, silicon nitride, or the like. The filling rate is preferably in the range of 30 parts by mass to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable resin composition. In order to reduce the coefficient of expansion, it is more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more.

2. Semiconductor Device As a method for obtaining a semiconductor device from the curable resin composition of the present invention, the semiconductor encapsulating material is molded using a casting mold, a transfer molding machine, an injection molding machine, or the like, and then heated at 50 to 200° C. for 2 hours. A method of heating for up to 10 hours may be mentioned.

3. Prepreg As a method for obtaining a prepreg from the curable resin composition of the present invention, the curable resin composition obtained by blending an organic solvent to form a varnish is coated with a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth). , glass mat, glass roving cloth, etc.) and then heating at a heating temperature according to the type of solvent used, preferably at 50 to 170°C. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to 20% by mass to 60% by mass.

Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like. Although it can be appropriately selected depending on the application, for example, when further manufacturing a printed circuit board from a prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, or dimethylformamide. , the non-volatile content is preferably 40% by mass to 80% by mass.

4. Printed circuit board As a method for obtaining a printed circuit board from the curable resin composition of the present invention, the prepreg is laminated by a conventional method, appropriately overlaid with copper foil, and heated at 170 to 300 ° C. under a pressure of 1 to 10 MPa. A method of thermocompression bonding for 10 minutes to 3 hours can be used.

5. Build-up Substrate As a method for obtaining a build-up substrate from the curable resin composition of the present invention, a method including steps 1 to 3 can be mentioned. In step 1, first, the curable resin composition appropriately blended with rubber, filler, etc. is applied to a circuit board having a circuit formed thereon by using a spray coating method, a curtain coating method, or the like, and then cured. In step 2, if necessary, the circuit board to which the curable resin composition has been applied is drilled with a predetermined through hole or the like, treated with a roughening agent, and the surface is washed with hot water. Concavo-convex portions are formed on the substrate and plated with a metal such as copper. In step 3, the operations of steps 1 and 2 are repeated as desired to alternately build up resin insulating layers and conductor layers having a predetermined circuit pattern to form a buildup board. In the above process, it is preferable to form the through-hole portion after forming the outermost resin insulating layer. In addition, the build-up board of the present invention is obtained by heat-pressing a resin-coated copper foil obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up board by omitting the steps of forming a hardened surface and plating.

6. Build-up film As a method of obtaining a build-up film from the curable resin composition of the present invention, for example, after applying the curable resin composition on the support film, drying, the resin composition layer on the support film A method of forming When the curable resin composition of the present invention is used for a build-up film, the film is softened under the lamination temperature conditions (usually 70° C. to 140° C.) in the vacuum lamination method, and simultaneously with the lamination of the circuit board, it is applied to the circuit board. It is essential to exhibit fluidity (resin flow) that allows resin filling in existing via holes or through holes, and it is preferable to blend the above components so as to exhibit such properties.

Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to allow resin filling within this range. When both sides of the circuit board are laminated, it is desirable to fill the through holes by about half.

As a specific method for producing the build-up film described above, after preparing a resin composition in which an organic solvent is blended to form a varnish, the composition is applied to the surface of the support film, and then heated or hot air is applied. A method of drying the organic solvent by spraying or the like to form a layer of the resin composition may be used.

Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol. Carbitols, toluene, aromatic hydrocarbons such as xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the nonvolatile content is used in a proportion of 30% to 60% by mass. is preferred.

It should be noted that the thickness of the layer of the resin composition to be formed is usually required to be equal to or greater 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 of the resin composition in the present invention may be protected with a protective film to be described later. By protecting the surface of the resin composition layer with a protective film, it is possible to prevent the surface of the resin composition layer from being dusted or scratched.

The support film and protective film described above are polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; Paper patterns and metal foils such as copper foils and aluminum foils can be used. The support film and protective film may be subjected to release treatment in addition to mud treatment and corona treatment. Although the thickness of the support film is not particularly limited, it is usually 10 to 150 μm, preferably 25 to 50 μm. Also, the thickness of the protective film is preferably 1 to 40 μm.

The support film 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 is peeled off after the resin composition layer constituting the build-up film is cured by heating, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling after curing, the support film is normally subjected to a release treatment in advance.

A multilayer printed circuit board can be produced from the build-up film obtained as described above. For example, when the layer of the resin composition is protected by a protective film, after removing these, the layer of the resin composition is applied to one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. Laminate with The method of lamination may be a batch type or a continuous roll type. If necessary, the build-up film and the circuit board may be heated (preheated) before lamination. As for lamination conditions, it is preferable that the pressure bonding temperature (laminating temperature) is 70 to 140° C., and the pressure bonding pressure is 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

7. Fiber Reinforced Composite Material As a method for obtaining a fiber reinforced composite material (a sheet-like intermediate material in which reinforcing fibers are impregnated with a resin) from the resin composition of the present invention, each component constituting the resin composition is uniformly mixed and varnish is obtained. is prepared, then impregnated into a reinforcing base material made of reinforcing fibers, and then subjected to a polymerization reaction.

Specifically, the curing temperature at the time of carrying out such a polymerization reaction is preferably in the temperature range of 50 to 250°C. , preferably 120 to 200°C.

The reinforcing fibers may be twisted yarns, untwisted yarns, or non-twisted yarns, but untwisted yarns and non-twisted yarns are preferable because they achieve both moldability and mechanical strength of the fiber-reinforced plastic member. Furthermore, as for the form of the reinforcing fibers, those in which the fiber direction is aligned in one direction or a woven fabric can be used. The woven fabric can be freely selected from plain weave, satin weave, etc., depending on the site and application. Specifically, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc., which are excellent in mechanical strength and durability, may be used, and two or more of these may be used in combination. Among these, carbon fiber is particularly preferable because the strength of the molded article is excellent, and various types of carbon fiber such as polyacrylonitrile, pitch, and rayon can be used. Among them, a polyacrylonitrile-based one is preferable because a high-strength carbon fiber can be easily obtained. Here, the amount of reinforcing fibers used when impregnating a reinforcing base material made of reinforcing fibers with varnish to form a fiber-reinforced composite material is such that the volume content of the reinforcing fibers in the fiber-reinforced composite material is 40% to 85%. It is preferable that the amount is within the range of

8. Fiber-Reinforced Resin Molded Product As a method for obtaining a fiber-reinforced molded product (a molded product obtained by curing a sheet-like member in which reinforcing fibers are impregnated with a resin) from the resin composition of the present invention, a fiber aggregate is laid in a mold and the varnish is applied. Using either the hand lay-up method, the spray-up method, or the male or female type, in which multiple layers are laminated, impregnating the base material made of reinforcing fibers with varnish, stacking and molding, and applying pressure to the molded product. The vacuum bag method, in which a flexible mold is placed over it and airtightly sealed is vacuum (depressurized) molded, the SMC press method, in which a sheet of varnish containing reinforcing fibers is compression-molded in a mold, and the fibers are laid out. A method of manufacturing a prepreg by impregnating reinforcing fibers with the varnish by the RTM method or the like of injecting the varnish into a tandem mold, and baking the prepreg in a large-sized autoclave. The fiber-reinforced resin molded article obtained above is a molded article having reinforcing fibers and a cured product of the resin composition. Specifically, the amount of reinforcing fibers in the fiber-reinforced molded article is 40 mass. % to 70% by mass, and more preferably 50% to 70% by mass in terms of strength.

9. Conductive Paste A method of obtaining a conductive paste from the resin composition of the present invention includes, for example, a method of dispersing fine conductive particles in the curable resin composition. The conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive, depending on the type of fine conductive particles used.

EXAMPLES Next, the present invention will be described in detail with reference to examples and comparative examples. In the following, "parts" and "%" are based on mass unless otherwise specified. GPC was measured under the following conditions.

<GPC measurement conditions>
Measuring device: "HLC-8320 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
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" 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 the "GPC Workstation EcoSEC-WorkStation".
(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% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (50 μl).

< ¹³ C-NMR measurement conditions>
Device: AL-400 manufactured by JEOL Ltd.,
Measurement mode: decoupling with reverse gate,
Solvent: deuterated chloroform,
Pulse angle: 30° pulse,
Sample concentration: 30 wt%,
Accumulated times: 4000 times.

<MS measurement conditions>
The MS spectrum was measured using a double focusing mass spectrometer "AX505H (FD505H)" manufactured by JEOL Ltd.

Example 1
166 g (1 mol) of 4-t-butylcatechol, 64 g (0.6 mol) of benzaldehyde, and 230 g of xylene were charged and dissolved in a flask equipped with a thermometer, a condenser and a stirrer while purging with nitrogen gas. After raising the temperature to 140° C., 14 g (0.17 mol) of a 49% by mass sodium hydroxide aqueous solution was added, and the temperature was raised to 150° C. and reacted for 6 hours. After that, the temperature was raised to 200° C. while removing xylene and water, and the reaction was further performed for 18 hours. After completion of the reaction, 400 g of xylene was added, the mixture was cooled to 80° C., washed with water for neutralization, and washed with 200 g of water three times until the pH of the washing liquid became neutral. Then, the inside of the system was dehydrated by azeotropy, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain phenol resin (1). The hydroxyl equivalent of the obtained phenol resin (1) was 188 g/eq. The GPC chart of phenol resin (1) is shown in FIG. 1, the ¹³ C-NMR chart is shown in FIG. 2, and the MS spectrum is shown in FIG. GPC revealed that the content of the substance represented by the following structural formula was 66%.

Example 2
While purging a flask equipped with a thermometer, condenser, and stirrer with nitrogen gas, 188 g of the phenol resin (1) obtained in Example 1 (hydroxyl equivalent: 1.0 g/eq), 555 g (6.0 mol) of epichlorohydrin, 53 g of n-butanol was charged and dissolved. After heating to 50° C., 220 g (1.10 mol) of a 20% by mass aqueous sodium hydroxide solution was added over 3 hours, followed by further reaction at 50° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150°C. Next, 300 g of methyl isobutyl ketone and 50 g of n-butanol were added to and dissolved in the obtained crude epoxy resin. Further, 15 g of a 10% by mass sodium hydroxide aqueous solution was added to this solution and reacted at 80° C. for 2 hours, followed by washing with 100 g of water three times until the pH of the washing liquid became neutral. Then, the inside of the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain epoxy resin (2). The epoxy equivalent of the obtained epoxy resin was 376 g/eq. The GPC chart of the obtained epoxy resin (2) is shown in FIG. 4, the ¹³ C-NMR spectrum is shown in FIG. 5, and the FD-MS spectrum is shown in FIG. GPC revealed that the content of the substance represented by the following structural formula was 48%.

Comparative Synthesis Example 1
152 g (1.0 mol) of trimethylhydroquinone was dissolved in a mixed solvent of 500 g of toluene and 200 g of ethylene glycol monoethyl ether in a 1-liter four-necked flask equipped with a stirrer and a heating device. 4.6 g of p-toluenesulfonic acid was added to the solution, and 64 g (0.6 mol) of benzaldehyde was added dropwise while paying attention to heat generation. After cooling, the precipitated crystals were separated by filtration, washed repeatedly with water until they became neutral, and then dried to obtain a phenol resin (1').

Comparative Synthesis Example 2
An epoxy resin (2') was obtained in the same manner as in Example 2, except that the phenol resin (1) was changed to 187 g of the phenol resin (1') (hydroxyl equivalent: 1.0 g/eq). The epoxy equivalent of the obtained epoxy resin was 272 g/eq.

Examples 3 and 4, Comparative Examples 1 and 2
<Preparation of composition and cured product>
After blending the following compounds in the composition shown in Table 1, the mixture was melt-kneaded for 5 minutes at a temperature of 90° C. using a twin roll to prepare a desired curable resin composition. The abbreviations in Table 1 mean the following compounds.
・ Epoxy resin: cresol novolak type epoxy resin "N-655-EXP-S" epoxy equivalent 201 g / eq (manufactured by DIC Corporation)
・ Phenolic resin: phenolic novolac resin "TD-2131" hydroxyl equivalent: 104 g / eq (manufactured by DIC Corporation)
・TPP: triphenylphosphine ・Fused silica: spherical silica “FB-5602” manufactured by Denki Kagaku Co., Ltd. ・Silane coupling agent: γ-glycidoxytriethoxysilane “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd. ・Carnauba Wax: "PEARL WAX No. 1-P" manufactured by Denki Kagaku Co., Ltd.

<Liquidity>
The curable resin composition was injected into a test mold, and the spiral flow value was measured under conditions of a mold temperature of 150° C., an injection pressure of 70 kg/cm 2 and a curing time of 120 seconds.

<Measurement of shrinkage rate during molding>
Using a transfer molding machine (manufactured by Kotaki Seiki Co., Ltd., KTS-15-1.5C), the resin composition was injection molded under the conditions of a mold temperature of 150 ° C., a molding pressure of 9.8 MPa, and a curing time of 600 seconds. A test piece having a length of 110 mm, a width of 12.7 mm, and a thickness of 1.6 mm was produced. After that, the test piece was post-cured at 175° C. for 5 hours, the inner diameter of the mold cavity and the outer diameter of the test piece at room temperature (25° C.) were measured, and the shrinkage ratio was calculated by the following formula.
Shrinkage rate (%) = {(inner diameter of mold) - (longitudinal dimension of cured product at 25°C)}/(inner diameter of mold cavity at 175°C) x 100 (%)
These results are shown in Table 1.

Claims (11)

General formula (1) below

[In the formula, R ¹ , R ² and R ³ are each independently an alkyl group or an aralkyl group having 4 to 8 carbon atoms, l is any one of 0, 1 or 2, m is 0 or 1 and n is 0 or 1 (except when l = m = n = 0), R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms, or an aralkyl group and
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group ;
R ⁶ and R ⁸ are benzene rings,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
s indicates the number of repetitions and is an integer of 0-10. ]
A xanthene-type phenol resin characterized by being represented by 2. The xanthene-type phenolic resin according to claim 1 , which has a hydroxyl equivalent in the range of 150 to 300 g/eq. 3. The xanthene-type phenolic resin according to claim 1, wherein the content of the compound where s=0 in the general formula (1) is in the range of 50 to 75% by area ratio in GPC measurement. General formula (2) below

[In the formula, R ¹ , R ² and R ³ are each independently an alkyl group or an aralkyl group having 4 to 8 carbon atoms, l is any one of 0, 1 or 2, m is 0 or 1 and n is 0 or 1 (except when l = m = n = 0), R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 4 to 8 carbon atoms, or an aralkyl group and
R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group or an aryl group ;
R ⁶ and R ⁸ are benzene rings,
p, q, and r are each independently 0 or 1 (except when p=q=r=0),
G is a glycidyl group, s is an integer of 0 to 10 and represents the number of repetitions. ]
A xanthene-type epoxy resin characterized by being represented by 5. The xanthene type epoxy resin according to claim 4 , which has an epoxy equivalent in the range of 300 to 500 g/eq. 6. The xanthene-type epoxy resin according to claim 4 or 5 , wherein the content of the compound where s=0 in the general formula (2) is in the range of 30 to 50% by area ratio in GPC measurement. A curable resin composition comprising the xanthene-type phenolic resin according to any one of claims 1 to 3 and a curing agent (X) as essential components. A curable resin composition comprising the xanthene-type epoxy resin according to any one of claims 4 to 6 and a curing agent (Y) as essential components. A cured product of the curable resin composition according to claim 7 or 8 . A semiconductor sealing material comprising the curable resin composition according to claim 7 or 8 and an inorganic filler. A semiconductor device, which is a cured product of the semiconductor encapsulating material according to claim 10 .

Images