JPWO2010087393A1 - Epoxy resin composition, method for producing the epoxy resin composition, and cured product thereof - Google Patents

Abstract

Excellent in low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, fast curing, flame retardancy, etc., especially for electrical and electronic industries, for sealing electronic components, and for laminated board materials It is an object of the present invention to provide an epoxy resin composition, a production method thereof, and an application thereof. This problem is obtained by the reaction of a phenol resin and an epihalohydrin having both an alkylene type polymer unit and a phenol novolak polymer unit in the molecule, and a ratio of the degree of polymerization of the both in a specific range. This is solved by an epoxy resin composition having a content ratio of 50% or less.

Description

  The present invention relates to an epoxy resin composition having low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, rapid curing and flame retardancy, a method for producing the same, and a cured product thereof.

  Epoxy resin compositions are widely used in the fields of electric / electronic parts, structural materials, adhesives, paints and the like due to workability and excellent electrical properties, heat resistance, adhesion, moisture resistance, etc. of the cured product.

  However, in recent years, with the development in the field of electrical and electronic materials, various properties such as flame retardancy, heat resistance, moisture resistance, adhesion, dielectric properties, etc., as well as low viscosity for high filler filling, have been developed. There is a need for improvement. Many proposals have been made for epoxy resin compositions for these requirements, but they are still not sufficient. Particularly in electronic circuit board materials, defects due to moisture absorption such as cracks during mounting solder treatment are a major problem, and there is a strong demand for low moisture absorption materials. In order to reduce the moisture absorption rate, it is necessary to increase the filling of the filler. To increase the filling, it is necessary to reduce the viscosity of the resin composition. On the other hand, carbon fiber reinforced composite materials that use carbon fibers with excellent specific strength and specific elastic modulus as reinforcing fibers and epoxy resin compositions with good wettability and adhesion with the carbon fibers as matrix resins also have low viscosity. There is a demand for a resin composition having heat resistance.

  The epoxy resin composition has an excellent performance that the warpage of the package is small when used in a single-side sealed package such as BGA (Ball Grid Array). However, in recent semiconductor packages, for example, in the case of BGA, it becomes a finer pitch or a batch sealing type, and it is required that the fluidity is high in addition to the small warpage and the adhesiveness with the substrate surface is good. ing. Further, if the melt viscosity is low, the fluidity and adhesion are improved, and a large amount of filler can be added, which is advantageous in terms of solder heat resistance and water resistance. That is, in order to satisfy the required properties for these encapsulants, a low melt viscosity epoxy resin composition that combines low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, fast curing, and flame retardancy The appearance of things is strongly desired.

  In addition, an epoxy resin composition having excellent water resistance and high adhesiveness at a high glass transition temperature is also desired as an interlayer insulating material for build-up substrates. To achieve this, water resistance and storage stability are inherently required. It is desired to have a phenolic curing agent having excellent low melting viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, rapid curing, and flame retardancy.

  Epoxy resins are often used as resin materials for electronic materials, and various phenol novolac condensates, amines, and acid anhydrides are used as curing agents for the epoxy resins. In particular, as a curing agent for epoxy resin for semiconductor (IC) sealing, phenolic novolak condensates are mainly used in terms of heat resistance and reliability. In recent years, ICs have been highly integrated, packages have become smaller and thinner, and surface mounting methods have been applied, and the sealing material has further improved thermal shock resistance and soldering heat resistance during surface mounting operations. It is requested. A major factor affecting the soldering heat resistance is the hygroscopicity of the sealing resin material. That is, the moisture-absorbing sealing material generates an internal pressure due to vaporization of water at a high temperature during the surface mounting operation, causes internal peeling and package cracks, and has poor soldering heat resistance. Accordingly, the epoxy resin is particularly required to have a low hygroscopic property.

  The epoxy resin varnish for insulating a printed circuit board preferably has a lower viscosity in view of handling at the time of prepreg production, and the smaller the amount of organic solvent used, the better. However, there is a problem that the viscosity of the epoxy resin solution used so far in this field cannot be sufficiently lowered or it is difficult to reduce the amount of the organic solvent used.

  On the other hand, as a method of reducing the hygroscopicity of the sealing material, there is a method of increasing the amount of filler such as non-hygroscopic silica filled in the sealing resin material. In this case, if the base resin material has a high viscosity, the high filling property of the filler is impaired. Therefore, it is desirable that the epoxy resin has a low viscosity. In addition, the sealing material is required to have heat resistance, high strength, toughness, flame retardancy, adhesive strength, and the like. Conventional sealing resin materials using a phenol novolak condensate as a curing agent for the sealing epoxy resin have a relatively high hygroscopicity and are not sufficiently satisfactory from the viewpoint of other physical properties.

Therefore, various phenol novolak condensates and their reaction products with epihalohydrins have been proposed in order to improve low hygroscopicity, heat resistance, adhesion, flame retardancy, and the like. For example, there are novolak condensates using alkylphenols such as o-cresol and novolak condensates using naphthols such as 1-naphthol (for example, Patent Documents 1 to 3). reference). Further, a phenolic compound using di (hydroxypropyl) biphenyl as a phenol condensing agent is disclosed (see Patent Document 4), and a phenol novolak condensate using a bis (methoxymethyl) biphenyl mixture. (Refer to Patent Document 5). Furthermore, an epoxy resin molding material for electronic component sealing (see Patent Document 6) that effectively uses formaldehyde is disclosed.
However, a material having further improved hygroscopicity, heat resistance, adhesive properties, flame retardancy, rapid curing, storage stability, and the like is desired.

JP 59-230017 Japanese Patent Laid-Open No. 05-078337 JP 05-086156 A JP 05-117350 A Japanese Patent Laid-Open No. 08-143648 JP-A-63-022824

  The object of the present invention is excellent in low melt viscosity, high glass transition temperature, low hygroscopicity, high adhesion, heat resistance, fast curing, flame retardancy, etc., especially for electrical and electronic industries, for sealing electronic components Another object of the present invention is to provide an epoxy resin composition for laminated board materials, a method for producing the epoxy resin composition, and a cured resin obtained from the epoxy resin composition.

  As a result of intensive investigations to obtain an epoxy resin composition having low moisture absorption, high adhesion, and heat-resistant physical properties of the aralkyl type phenol resin and having a low melt viscosity, the present inventors have found that an alkylene type in the molecule. By having both a polymer unit and a phenol novolak polymer unit, and making the ratio of the degree of polymerization of the both within a specific range, low melt viscosity and fast curing, low moisture absorption, high adhesion, and excellent heat resistance The present inventors have found that a phenol novolac resin composition can be obtained, and found that an excellent epoxy resin composition can be obtained by the reaction of the obtained resin composition with epihalohydrin, thereby completing the present invention.

  That is, this invention contains the component represented by following General formula (1), and the content rate of the compound represented by the following general formula (3-1) and general formula (3-2) is 50% or less It is a resin composition.

General formula (1):

(In the formula, R represents the following general formula (2-1) and general formula (2-2):

で示されるビフェニリレン基及びキシリレン基から選ばれる少なくとも一つの架橋基を表し、Ｒ^１、Ｒ^２及びＲ^３は同一でも異なっていてもよく、それぞれ、水素原子、炭素数１〜６個のアルキル基、又はアリール基であり、ｐ、ｑ、ｒはそれぞれ０〜２の整数である。また、ｍおよびｎは、正の数値であり、Ｇはグリシジル基を表す。）

Represents at least one bridging group selected from a biphenylylene group and a xylylene group, and R ¹ , R ² and R ³ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or an aryl group, and p, q and r are each an integer of 0 to 2. M and n are positive numerical values, and G represents a glycidyl group. )

（式中、Ｇはグリシジル基を表し、Ｒ^４，Ｒ^５は同一でも異なっていてもよく、それぞれ、水素原子、炭素数１〜６個のアルキル基又はアリール基を表す。）General formula (3-1) and (3-2):

(In the formula, G represents a glycidyl group, and R ⁴ and R ⁵ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group.)

  Furthermore, it is the said epoxy resin composition whose m / n is 0.04-20 and whose melt viscosity in 150 degreeC is 10-200 mPa * s.

（式中、Ｒは下記一般式（２−１）及び一般式（２−２）：Further, the present invention provides the following general formula (4):

(In the formula, R represents the following general formula (2-1) and general formula (2-2):

で示されるビフェニリレン基及びキシリレン基から選ばれる少なくとも一つの架橋基を表し、Ｒ^１、Ｒ^２及びＲ^３は同一でも異なっていてもよく、それぞれ、水素原子、炭素数１から６個のアルキル基又はアリール基であり、ｐ、ｑ、ｒはそれぞれ０〜２の整数である。また、ｍおよびｎは、正の数値を示す。）で表される成分を含有するフェノール樹脂組成物とエピハロヒドリンをアルカリ金属水酸化物の存在下において反応させることを特徴とするエポキシ樹脂組成物の製造方法である。

And represents at least one bridging group selected from a biphenylylene group and a xylylene group, and R ¹ , R ² and R ³ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or it is an aryl group, and p, q, and r are integers of 0-2, respectively. M and n represent positive numerical values. The epoxy resin composition is produced by reacting a phenol resin composition containing a component represented by (II) with an epihalohydrin in the presence of an alkali metal hydroxide.

Furthermore, this invention is the epoxy resin hardened | cured material which hardened the said epoxy resin composition.
Moreover, the epoxy resin composition of the present invention comprises a biphenylylene compound represented by the general formula (6-1) described below and / or a xylylene compound represented by the general formula (6-2) described below, a phenol compound, It is an epoxy resin composition obtained by reacting an epihalohydrin with a phenol resin composition obtained by reacting formaldehyde.

The epoxy resin composition of the present invention comprises a biphenylylene group such as 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group, 1,4-xylylene group, It has both polymer units of an epoxy resin containing at least one crosslinking group selected from a xylylene group such as a 2-xylylene group and a 1,3-xylylene group and an epoxy resin containing a methylene crosslinking group. By having a structure in which the ratio is in a specific range, suitable for epoxy resin compositions, low melt viscosity, high glass transition temperature, low moisture absorption, high adhesion, heat resistance, and flame retardancy, storage stability, It is a resin composition having good handleability.
The resin composition of the present invention can be applied to the latest semiconductor sealing materials such as BGA.

The epoxy resin composition of the present invention is a phenol having a total of n polymerization units of a phenol resin in which R represented by the general formula (4) contains a biphenylylene cross-linking group and / or a xylylene cross-linking group, and a methylene cross-linking group. An epoxy resin composition containing a component of the above general formula (1) obtained by glycidyl etherification of a copolymer-type phenol resin composition having a total of m polymerized units of resin using epihalohydrin, preferably The polymerization degree ratio m / n of each polymer unit in the formula (1) is 0.04 to 20, more preferably 0.05 to 9, further preferably 0.1 to 6, and the melt viscosity at 150 ° C. The epoxy resin composition has a viscosity of 5 to 1000 mPa · s, preferably 10 to 200 mPa · s. It is preferable that m / n is 0.04 to 20 and the melt viscosity at 150 ° C. is 10 to 200 mPa · s.
The preferred range differs depending on the average molecular weight of the epoxy resin composition (degree of polymerization: depending on the molar ratio of the phenol compound used and the total amount of the cross-linked product and formaldehyde constituting R in the general formula (4)).
About the phenol resin composition shown by the said General formula (4), the detail is described in Unexamined-Japanese-Patent No. 2008-189708.

A phenol resin composition in which the molar ratio of the phenol compound to be used and the total amount of the cross-linked product and formaldehyde constituting R in the general formula (4) is 2.0 to 3.0 times less than glycidyl ether The melted epoxy resin composition has a melt viscosity at 150 ° C. of 100 to 200 mPa · s, more preferably 100 to 150 mPa · s.
When the molar ratio of the phenol compound used and the total amount used of the cross-linked product and formaldehyde constituting R in the general formula (4) is 3.0 or more and less than 10 times, preferably 3.0 to 5 times. In the epoxy resin composition obtained by glycidyl etherification of the phenol resin composition in the case of mol, the melt viscosity at 150 ° C. is 10 to 100 mPa · s, more preferably 30 to 80 mPa · s.

  The epoxy resin composition of the present invention is not particularly limited with respect to the value of m / n, but if the value of m / n is less than 0.04, the effect of lowering the melt viscosity may be insufficient, and the fluidity May not improve. Therefore, the value of m / n is preferably 0.04 or more. More preferably, it is 0.1-6. A preferable range of the molar ratio (phenol / (m + n)) of the phenol compound and the total use amount of the crosslinked body and formaldehyde constituting R of the general formula (4) is 2.0 to 5, and this is taken into consideration. The preferable value of m / n is 0.1-6, and a more preferable range is 0.3-3.

As described in the general formula (4), the phenol compound used in the present invention has at least one hydroxyl group on the benzene ring, and R ¹ , R ² and R ³ may be the same or different, and each is a hydrogen atom. , An alkyl group having 1 to 6 carbon atoms or an aryl group, and p, q and r are a group of compounds each consisting of an integer of 0 to 2. Examples of the alkyl group having 1 to 6 carbon atoms include linear alkyl groups such as methyl group, ethyl group, and propyl group, and branched alkyl groups such as isopropyl group and tertiary butyl group. Includes a phenyl group.
There is no problem even if these phenol compounds are used alone or in combination of two or more.
Specific phenol compounds include, for example, monohydric phenols such as phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, nonylphenol, xylenol, and butylmethylphenol, and divalent phenols such as catechol, resorcin, and hydroquinone. Among them, phenol is particularly preferable.

As the compound that forms a methylene crosslinking group in the present invention, formaldehyde is preferably exemplified. Furthermore, the form of formaldehyde is not particularly limited, but a formaldehyde aqueous solution and a polymer that decomposes in the presence of an acid such as paraformaldehyde and trioxane to formaldehyde can also be used.
A formaldehyde aqueous solution that is easy to handle is preferable, and a commercially available 42% formaldehyde aqueous solution can be used as it is.

  The bridging group R used in the present invention is a 4,4′-biphenylylene group, a 2,4′-biphenylylene group, or a 2,2 ′ represented by the following general formula (2-1) and general formula (2-2). -Biphenylylene group, 1,4-xylylene group, 1,2-xylylene group, 1,3-xylylene group and the like can be mentioned. These isomers can be used alone or in combination.

これらの架橋基は、次式（６−１）及び（６−２）で表される化合物から誘導される。

These crosslinking groups are derived from compounds represented by the following formulas (6-1) and (6-2).

（ここで、式中、Ｙはハロゲン原子、ヒドロキシル基又は炭素原子数１〜６のアルコキシル基を表す。）
ここで、ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素が挙げられるが、塩素が好ましい。アルコキシル基としては、特に制限はないが、炭素数１〜６個の脂肪族アルコキシが好ましい。
式（６−１）及び（６−２）で表される化合物は、具体的には、４，４’−ジ（ハロゲノメチル）ビフェニル、２，４’−ジ（ハロゲノメチル）ビフェニル、２，２’−ジ（ハロゲノメチル）ビフェニル、４，４’−ジ（アルコキシメチル）ビフェニル、２，４’−ジ（アルコキシメチル）ビフェニル、２，２’−ジ（アルコキシメチル）ビフェニル、１，４−ジ（ハロゲノメチル）ベンゼン、１，４−ジ（アルコキシメチル）ベンゼン、１，２−ジ（ハロゲノメチル）ベンゼン、１，２−ジ（アルコキシメチル）ベンゼン、１，３−ジ（ハロゲノメチル）ベンゼンおよび１，３−ジ（アルコキシメチル）ベンゼン、あるいは、４，４’−ジ（ヒドロキシメチル）ビフェニル、２，４’−ジ（ヒドロキシメチル）ビフェニル、２，２’−ジ（ヒドロキシメチル）ビフェニル、１，４−ジ（ヒドロキシメチル）ベンゼン、１，３−ジ（ヒドロキシメチル）ベンゼンおよび１，２−ジ（ヒドロキシメチル）ベンゼンである。
式（６−１）及び（６−２）で表される化合物の好ましい具体的な化合物としては、４，４’−ジ（クロロメチル）ビフェニル、４，４’−ジ（メトキシメチル）ビフェニル、４，４’−ジ（エトキシメチル）ビフェニル、１，４−ジ（クロロメチル）ベンゼン、１，４−ジ（メトキシメチル）ベンゼン及び１，４−ジ（エトキシメチル）ベンゼンが挙げられる。
これら、（４）式中のＲを構成する架橋体としては、ビフェニリレン基および／又はキシリレン基を単一でも混合して使用することも何ら問題ではない。しかし、混合して使用する場合では、その混合比率は、ビフェニリレン基１モルに対して２０〜５０モル％でキシリレン基を使用するのが好ましい。Ｒがビフェニリレン架橋基、特に４，４‘−ビフェニリレン架橋基を有することが好ましい。

(Wherein, Y represents a halogen atom, a hydroxyl group, or an alkoxyl group having 1 to 6 carbon atoms.)
Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine, with chlorine being preferred. Although there is no restriction | limiting in particular as an alkoxyl group, A C1-C6 aliphatic alkoxy is preferable.
Specifically, the compounds represented by formulas (6-1) and (6-2) include 4,4′-di (halogenomethyl) biphenyl, 2,4′-di (halogenomethyl) biphenyl, 2, 2′-di (halogenomethyl) biphenyl, 4,4′-di (alkoxymethyl) biphenyl, 2,4′-di (alkoxymethyl) biphenyl, 2,2′-di (alkoxymethyl) biphenyl, 1,4- Di (halogenomethyl) benzene, 1,4-di (alkoxymethyl) benzene, 1,2-di (halogenomethyl) benzene, 1,2-di (alkoxymethyl) benzene, 1,3-di (halogenomethyl) benzene And 1,3-di (alkoxymethyl) benzene, or 4,4′-di (hydroxymethyl) biphenyl, 2,4′-di (hydroxymethyl) biphenyl, 2,2′-di (hydroxyme Le) biphenyl, 1,4-di (hydroxymethyl) benzene, 1,3-di (hydroxymethyl) benzene and 1,2-di (hydroxymethyl) benzene.
Preferred specific compounds of the compounds represented by formulas (6-1) and (6-2) include 4,4′-di (chloromethyl) biphenyl, 4,4′-di (methoxymethyl) biphenyl, 4,4′-di (ethoxymethyl) biphenyl, 1,4-di (chloromethyl) benzene, 1,4-di (methoxymethyl) benzene and 1,4-di (ethoxymethyl) benzene.
As the cross-linked product constituting R in the formula (4), it is not a problem to use a biphenylylene group and / or a xylylene group alone or in combination. However, in the case of using a mixture, it is preferable to use the xylylene group at a mixing ratio of 20 to 50 mol% with respect to 1 mol of the biphenylylene group. R preferably has a biphenylylene cross-linking group, particularly a 4,4′-biphenylylene cross-linking group.

About the manufacturing conditions of a phenol resin composition, since the detail is described in Unexamined-Japanese-Patent No. 2008-189708, what is necessary is just to implement according to the conditions.
An example of the manufacturing method of the phenol resin composition shown in General formula (4) is shown below.

  In the phenol resin composition, the content ratio of the compounds represented by the following general formulas (5-1) and (5-2) (sometimes collectively referred to as “binuclear bodies”) is the phenol resin. On the other hand, it is preferably 50% or less, particularly 47% or less, more preferably 5 to 47%, and particularly preferably 10 to 40%. In addition, the content rate of the compound represented by general formula (5-1) and general formula (5-2) is calculated | required from the area ratio of the chart measured by gel permeation chromatography as mentioned later.

（式中、Ｒ^４，Ｒ^５は同一でも異なっていてもよく、それぞれ、水素原子、炭素数１〜６個のアルキル基又はアリール基を表す。）
一般式（５−１）及び一般式（５−２）のＲ^４，Ｒ^５における炭素数１〜６個のアルキル基としては、メチル基、エチル基、プロピル基等の直鎖状アルキル基、イソプロピル基、ターシャリーブチル基等の分岐鎖状アルキル基などが挙げられ、アリール基としては、フェニル基などが挙げられる。

(In the formula, R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group.)
Examples of the alkyl group having 1 to 6 carbon atoms in R ⁴ and R ⁵ in the general formula (5-1) and the general formula (5-2) include linear alkyl groups such as a methyl group, an ethyl group, and a propyl group, Examples thereof include branched alkyl groups such as isopropyl group and tertiary butyl group, and examples of aryl groups include phenyl group.

[Production of phenolic resin composition]
In the method for producing the phenol resin composition represented by the general formula (4), n-fold moles of R, that is, 4,4′-biphenylylene group or 2,4,4 with respect to a certain amount of phenol compound in the presence of an acid catalyst. A cross-linked product containing a '-biphenylylene group, 2,2'-biphenylylene group and / or 1,4-xylylene group, 1,2-xylylene group, 1,3-xylylene group or the like and m-fold mol of formaldehyde They can be added simultaneously and carried out in a single-stage condensation reaction.
In this case, there is no particular restriction on the amount of phenol used relative to the total of 1 mol of the cross-linked product and formaldehyde constituting R in the general formula (4), but preferably 1.3 to 10 times mol, more preferably Is used in the range of 2.0 to 5 moles, and the phenol compound and formaldehyde are preferentially reacted at a low reaction temperature (for example, around 100 ° C. as an example), and mainly a low molecular weight methylene crosslinking group phenol resin. It is preferable to employ a system in which the composition is formed, and then the methylene crosslinking group phenol resin composition, the crosslinked body constituting R in the general formula (4), and the phenol are reacted by raising the temperature or increasing the catalyst.
The acid catalyst to be used is not particularly limited, and known ones such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid can be used alone or in combination of two or more. Toluenesulfonic acid is particularly preferred.
The temperature of the condensation reaction is 50 to 120 ° C., preferably 80 to 110 ° C. as a low temperature condition, and the reaction temperature at the time of temperature rise is 130 to 230 ° C., preferably 150 to 200 ° C.
The time for the condensation reaction varies depending on the reaction temperature and the type and amount of the catalyst used, but is about 1 to 24 hours.
The reaction pressure is usually carried out under normal pressure, but there is no problem even if it is carried out under slight pressure or reduced pressure.
When the amount of phenol used is less than 1.3 moles per 1 mole of the total of the cross-linked product and formaldehyde constituting R in the general formula (4), a phenol resin composition having a high molecular weight and a high melt viscosity is obtained. The tendency to be recognized is recognized.
In addition, when the amount of phenol used is more than 10 times mole, low molecular weight components of 2 nuclei or less increase, Tg and mechanical strength decrease tend to decrease physical properties. Increasing costs and problems in terms of environmental impact. The amount of phenol used is preferably 1.5 to 10 moles.

  The phenol resin composition used in the present invention is a phenol compound, formaldehyde, 4,4′-biphenylylene group or 2,4′-biphenylylene group constituting R in the general formula (4), or 2,2 There is no limitation on the addition order of the cross-linked product such as' -biphenylylene group and / or 1,4-xylylene group, 1,2-xylylene group, 1,3-xylylene group, etc. It is desirable from the viewpoint of economy and productivity.

As another method, formaldehyde of the crosslinked product and 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1 constituting R in the general formula (4) A method of shifting the addition order of a crosslinked product such as a 1,4-xylylene group, a 1,2-xylylene group, or a 1,3-xylylene group is also included.
Specifically, a phenol compound and formaldehyde are previously condensed in the presence of an acid catalyst, and then a 4,4′-biphenylylene group or a 2,4′-biphenylylene group constituting R in the general formula (4) , 2,2'-biphenylylene group and / or 1,4-xylylene group, or 1,2-xylylene group or 1,3-xylylene group, etc. You can also In such a two-stage condensation reaction, a phenol compound can be newly added in the second-stage reaction. However, in this case as well, it is preferable to use an excessive amount of the phenol compound as in the case of the one-stage reaction. The phenol resin added in the second stage reaction is a total of 1 to 2 stages with respect to a total of 1 mol of the cross-linked product and formaldehyde constituting R in the general formula (4) charged in the total of the 1 to 2 stage reactions. It is particularly preferable to use phenol in a range of 1.3 mol times or more, preferably 2.3 to 5 times mol. When carried out in such a two-stage reaction, the degree of polymerization of each polymer unit of the alkylene group-containing crosslinkable phenol resin and the methylene crosslinkable group-containing phenol resin, that is, the distribution of n and m becomes narrow, and the control of the molecular weight becomes easy. It is preferred for the purposes of the present invention because a polymer of the desired melt viscosity is easily obtained.
However, a phenol compound, 4,4′-biphenylylene group, 2,4′-biphenylylene group, 2,2′-biphenylylene group and / or 1,4-xylylene group constituting R in the general formula (4) Alternatively, formaldehyde can be added after the reaction of the crosslinked product such as 1,2-xylylene group or 1,3-xylylene group. In this case, the total amount of the phenol compound is charged in the formula (1) When the synthesis is carried out in the vicinity of 1.3 times moles with respect to the total of 1 mole of the cross-linked product and formaldehyde constituting R, there is a case where unfavorable cases occur because the polymerization progresses and the viscosity does not progress.

The two-stage condensation reaction can be carried out according to the one-stage condensation reaction conditions.
The amount of the acid catalyst used in the one-stage condensation reaction and the two-stage condensation reaction varies depending on the type, but in the case of oxalic acid, it is about 0.1 to 2.0% by weight, and in the case of sulfuric acid, 0.05 to 0.00. About 5% by weight, and in the case of paratoluenesulfonic acid, it is preferable to use about 0.02 to 0.1% by weight. In particular, when a two-stage condensation reaction is performed, it is preferable to use sulfuric acid or paratoluenesulfonic acid when the second-stage biphenylylene group or xylylene group-containing crosslinked product is reacted with a phenol compound and a methylene crosslinking group phenol resin. . The reaction temperature is not particularly limited, but is preferably set in the range of about 60 to 160 ° C. More preferably, it is 80-140 degreeC.

After the condensation reaction in the presence of an acid catalyst, the phenol resin composition used in the present invention can be obtained by removing the unreacted phenol compound and the acid catalyst.
As a method for removing a phenol compound, a method is generally employed in which heat is applied under reduced pressure or while blowing an inert gas to distill the phenol compound out of the system. The removal of the acid catalyst includes a method such as washing with water.

  The epoxy resin composition of the present invention has a content ratio of compounds represented by the following general formula (3-1) and general formula (3-2) (these may be collectively referred to as “binuclear bodies”). It is necessary to be 50% or less with respect to the epoxy resin, particularly preferably 47% or less, more preferably 5 to 47%, and particularly preferably 10 to 40%. In addition, the content rate of the compound represented by general formula (3-1) and general formula (3-2) is calculated | required from the area ratio of the chart measured by the gel permeation chromatography as mentioned later.

（式中、Ｇはグリシジル基を表し、Ｒ^４，Ｒ^５は同一でも異なっていてもよく、それぞれ、水素原子、炭素数１〜６個のアルキル基又はアリール基を表す。）
Ｒ^４，Ｒ^５の炭素数１〜６個のアルキル基としては、メチル基、エチル基、プロピル基等の直鎖状アルキル基、イソプロピル基、ターシャリーブチル基等の分岐鎖状アルキル基などが挙げられ、アリール基としては、フェニル基などが挙げられる。

(In the formula, G represents a glycidyl group, and R ⁴ and R ⁵ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group.)
Examples of the alkyl group having 1 to 6 carbon atoms of R ⁴ and R ⁵ include a linear alkyl group such as a methyl group, an ethyl group, and a propyl group, and a branched alkyl group such as an isopropyl group and a tertiary butyl group. Examples of the aryl group include a phenyl group.

  In the epoxy resin composition of the present invention, when the content ratio of the compounds represented by the general formula (3-1) and the general formula (3-2) exceeds 50%, the ICI viscosity at 150 ° C. of the epoxy resin composition is The viscosity becomes so high that it cannot be measured. For this reason, the handleability of an epoxy resin composition worsens.

[Production of epoxy resin composition]
In the method for producing the epoxy resin composition represented by the general formula (1), the phenol resin composition represented by the general formula (4) is subjected to epihalohydrin in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. It can be obtained by glycidyl etherification at 10 ° C to 120 ° C. For this glycidyl etherification, a conventionally known method can be used and is not particularly limited.
As epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin, epibromohydrin, etc. can be used. preferable.

  The usage-amount of epihalohydrin is not specifically limited, Although it can select suitably according to the molecular weight of the target epoxy resin, Usually, an excess amount is used with respect to a phenol resin. Since the epoxy resin composition of the present invention is desired to have a low melt viscosity, the amount of epichlorohydrin used is 3.0 to 20 moles, preferably 3.0 to 10 moles per mole of the phenolic resin composition hydroxyl group. Is a mole.

  The alkali metal hydroxide used may be a solid or an aqueous solution thereof. In the case of using an aqueous solution, while continuously adding an aqueous solution of an alkali metal hydroxide into the reaction system, water and epihalohydrin are allowed to flow out of the reaction system continuously under reduced pressure or normal pressure to remove moisture. A method may be used in which the removed epihalohydrin is continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.8-2.0 mol with respect to 1 mol of phenol resin composition hydroxyl groups, Preferably it is 0.9-1.3 mol.

  In the glycidyl etherification, the reaction is preferably carried out by adding an alcohol such as methanol, ethanol or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran or dioxane.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a mixture of the phenol resin composition represented by the general formula (4) and epihalohydrin, and obtained by these reactions. A method of adding an alkali metal hydroxide to the halohydrin etherified product to cause ring closure may be used.

  Although reaction temperature does not have a restriction | limiting in particular, Usually, it is 30-90 degreeC, Preferably it is 35-80 degreeC.

  Although the reaction time is affected by the reaction temperature, it is usually 0.5 to 10 hours, preferably 1 to 8 hours.

  After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure.

  In order to reduce hydrolyzable chlorine, the recovered crude epoxy resin composition is dissolved in a solvent such as toluene or methylid butyl ketone, and an aqueous solution of alkali metal hydroxide is added and reacted to cause ring closure. You can be sure.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin composition represented by the general formula (1) of the present invention.

A curing agent and a curing accelerator can be added to the epoxy resin composition of the present invention. It is preferable that the addition amount of a hardening | curing agent is 5-40 weight part with respect to 100 weight part of epoxy resins, and it is more preferable that it is 5-20 weight part. The addition amount of the curing accelerator is preferably 0.01 to 10 parts by weight and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.
Hereinafter, the curing agent and the curing accelerator are described.

[Curing agent]
Examples of the curing agent to be used include phenol compounds, amine compounds, acid anhydride compounds, amide compounds, and the like.

  Specific curing agents that can be used include amine curing agents such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, polyalkylene glycol polyamine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, dimer of linolenic acid and ethylenediamine. Amide-based curing agents such as polyamide resin to be synthesized, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride , Acid anhydride curing agents such as methylhexahydrophthalic anhydride, phenol novolak resin, cresol novolak resin, bisphenol A type novolak resin, bisphenol F type novolak resin, aroma Hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol aralkyl resin, phenol trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol -Phenolic co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, aminotriazine-modified phenol resins and the like, and their modified products, imidazole, BF3-amine complexes In addition, guanidine derivatives and the like can be mentioned, but not limited thereto.

[Curing accelerator]
As a hardening accelerator, the well-known hardening accelerator for hardening an epoxy resin composition with a phenol type hardening | curing agent can be used. Examples of such curing accelerators include organic phosphine compounds and their boron salts, tertiary amines, quaternary ammonium salts, imidazoles and their tetraphenylboron salts, and among them, curability and moisture resistance. From this point, triphenylphosphine and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) are preferable. In order to achieve higher fluidity, a heat-latent curing accelerator that exhibits activity by heating is more preferable, and tetraphenylphosphonium derivatives such as tetraphenylphosphonium and tetraphenylborate are preferable.

[Other additives]
In the epoxy resin composition of the present invention, an inorganic filler, a release agent, a colorant, a flame retardant, a low stress agent, or the like can be added or reacted in advance as necessary. Especially when used for semiconductor encapsulation, the addition of inorganic fillers is essential. Examples of such inorganic fillers include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, magnesia, barium sulfate and the like. However, amorphous silica, crystalline silica and the like are particularly preferable. The usage-amount of these additives may be the same as the usage-amount in the conventional epoxy resin composition for semiconductor sealing.

[Hardened product of epoxy resin composition]
The epoxy resin composition of the present invention can be a cured product. A cured product of the epoxy resin composition is obtained by mixing the epoxy resin composition of the present invention, a phenol resin composition as a curing agent, and a curing accelerator, and curing the mixture in a temperature range of 100 to 250 ° C. can get.
Moreover, hardened | cured material can also be obtained by hardening the epoxy resin composition of this invention in the temperature range of 100-250 degreeC.

The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. Moreover, the evaluation method of the resin composition obtained by this invention is shown below.
(1) Epoxy equivalent It measured by the method based on JISK-7236.
(2) 150 ° C. melt viscosity: The melt viscosity of the epoxy resin composition at 150 ° C. was measured using an ICI melt viscometer.
The measuring method of ICI viscosity is as follows.
ICI Cone Plate Viscometer MODEL CV-1S TOA Industrial Co., Ltd.
The plate temperature of the ICI viscometer was set to 150 ° C., and a predetermined amount of the sample was weighed.
Place the weighed resin composition on the plate, press it with a cone from the top, and leave it for 90 seconds. The cone was rotated and its torque value was read as ICI viscosity.
(3) Gel time The epoxy resin composition and the phenol resin composition are charged into a test tube so as to have an equivalent of 1: 1, and TPP is measured to 0.12 wt% with respect to the epoxy, and then charged into the test tube. It is.
A test tube was installed in a gel timer (Toshiba Corp. time meter SF0-304M) in which the hot water temperature was set to 150 ° C. and 175 ° C., and a SUS stir bar was used to stir one rotation per second.
At first, the viscosity is low and liquid, but after a certain period of time, the viscosity of the resin composition rapidly increases and becomes a gel. This time was defined as gel time. The faster this time, the better the curability.
(4) Water absorption rate Each composition was 150 ° C. × 5 Hr. + 180 ° C. × 3 Hr. And then cured to the following size to prepare a sample.
Size: (φ50 ± 1) × (3 ± 0.2) (diameter × thickness: mm)
The surface of the sample was thoroughly wiped with a cloth, and the weight of the sample was measured.
The sample was placed in a 100 ml bottle and 80 ml of pure water was added.
The bottle was placed in a hot air circulating dryer at 95 ° C. × 24 Hr. I left it alone.
The bottle was taken out from the hot air circulation dryer, immersed in a low temperature constant temperature water bath and cooled to 25 ° C.
After cooling, the water adhering to the surface was well wiped and the weight was measured.
The water absorption was determined using the following equation.
Water absorption [%] = ((B−A) / A) × 100
A: Weight before water absorption [g]
B: Weight after water absorption [g]
(5) Tg (glass transition temperature)
Each composition was 150 ° C. × 5 Hr. + 180 ° C. × 3 Hr. A sample was prepared by casting, curing, and cutting to the following size.
Size: (50 ± 1) × (40 ± 1) × (100 ± 1) (length × width × height; mm)
The sample was set in a thermomechanical analyzer (TMA-60 (manufactured by SHIMADZU)) and measured in an N ₂ atmosphere.
The measurement was performed at a heating rate = 5 ° C./min. Was measured up to 350 ° C., and the temperature at the inflection point was determined and used as the glass transition temperature (Tg).
(6) Strength Measured according to JIS K 7171.
(7) Spiral flow Using a low-pressure transfer molding machine, a spiral flow measurement mold conforming to EMMI-1-66 was subjected to EMC under the conditions of a mold temperature of 175 ° C, an injection pressure of 6.8 MPa, and a holding time of 120 seconds. The composition was injected and the flow length was measured.
(8) Flame retardancy (UL-94)
It measured according to UL-94.

  A detailed synthesis example is shown below.

[Synthesis of phenolic resin composition]
Synthesis example 1
A glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube was charged with 564 g (6.00 mol) of phenol, 4,4′-di (methoxymethyl) biphenyl (hereinafter abbreviated as 4,4′-BMMB). 202.60 g (0.84 mol), 42% formalin aqueous solution 40.0 g (0.56 mol), and 50% sulfuric acid aqueous solution 0.28 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 330 g of a phenol resin composition.
The obtained phenol resin composition had an ICI viscosity of 39 mPa · s, and an OH equivalent by an acetylation method was 166 g / eq.

Synthesis example 2
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 470 g (5.00 mol), 4,4′-BMMB 233.44 g (0.96 mol), 42% formalin aqueous solution 45. 71 g (0.64 mol) and 50% sulfuric acid aqueous solution 0.26 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated and 360 g of a phenol resin composition was obtained by distilling off unreacted phenol by distillation under reduced pressure.
The obtained phenol resin composition had an ICI viscosity of 70 mPa · s, and an OH equivalent by an acetylation method was 164 g / eq.

Synthesis example 3
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 470 g (5.00 mol), 4,4′-BMMB 288.10 g (1.19 mol), 42% formalin aqueous solution 56. 43 g (0.79 mol) and 50% sulfuric acid aqueous solution 0.29 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 450 g of a phenol resin composition.
The obtained phenol resin composition had an ICI viscosity of 75 mPa · s, and an OH equivalent by an acetylation method was 171 g / eq.

Synthesis example 4
To a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 404.2 g (4.30 mol) of phenol, 4,4′-di (chloromethyl) biphenyl (hereinafter, 4,4′-BCMB) was added. 150.7 g (0.60 mol) was charged and reacted at 100 ° C. for 3 hours, and then 28.57 g (0.40 mol) of 42% formalin aqueous solution was added, and then reacted at 100 ° C. for 3 hours. I let you. Meanwhile, the hydrochloric acid produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 251 g of a phenol resin composition.
The obtained phenol resin composition had an ICI viscosity of 40 mPa · s, and an OH equivalent by an acetylation method was 166 g / eq.

Synthesis example 5
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 470 g (5.00 mol), 4,4′-BMMB 302.5 g (1.25 mol), 50% sulfuric acid aqueous solution 0. 28 g was charged and reacted for 2 hours while maintaining the reaction temperature at 125 ° C., then heated to 165 ° C. and reacted for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 380 g of a phenol resin composition.
The obtained phenol resin composition had an ICI viscosity of 115 mPa · s and an OH equivalent by an acetylation method of 202 g / eq.

Synthesis Example 6
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 470 g (5.00 mol), 4,4′-BMMB 389.1 g (1.61 mol), 50% sulfuric acid aqueous solution 0. 28 g was charged and reacted for 2 hours while maintaining the reaction temperature at 125 ° C., then heated to 165 ° C. and reacted for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 470 g of a phenol resin composition.
The obtained phenol resin composition had an ICI viscosity of 130 mPa · s and an OH equivalent by an acetylation method of 208 g / eq.

Synthesis example 7
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, phenol 274.5 g (2.92 mol), 4,4′-BMMB 290.4 g (1.23 mol), 42% formalin aqueous solution 57.14 g (0.82 mol) and 50% sulfuric acid aqueous solution 0.22 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was removed by distillation under reduced pressure to obtain 370 g of a phenol resin composition.
The obtained phenol resin composition had an ICI viscosity of 90 mPa · s, and an OH equivalent by an acetylation method was 188 g / eq.

Synthesis Example 8
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, phenol 685 g (7.27 mol), 4,4′-BMMB 151.15 g (0.62 mol), 42% formalin aqueous solution 29. 7 g (0.4 mol) and 50% sulfuric acid aqueous solution 0.34 g were charged and reacted at 100 ° C. for 3 hours.
Thereafter, the reaction was carried out for 2 hours while maintaining the reaction temperature at 125 ° C., then the temperature was raised to 165 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 250 g of a phenol resin composition.
The obtained phenol resin composition had an ICI viscosity of 40 mPa · s, and an OH equivalent by an acetylation method was 164 g / eq.

Synthesis Example 9
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 141 g (1.5 mol) of phenol, 248.6 g (1.03 mol) of 4,4′-BMMB, 50% aqueous sulfuric acid solution was added. 16 g was charged and reacted for 2 hours while maintaining the reaction temperature at 125 ° C., then heated to 165 ° C. and reacted for 3 hours. Meanwhile, the methanol produced was distilled off. After completion of the reaction, the obtained reaction solution was cooled and washed with water three times. The oil layer was separated, and 280 g of a phenol resin composition was obtained by distilling off unreacted phenol by distillation under reduced pressure.
The ICI viscosity of the obtained phenol resin composition was not measurable at 150 ° C., and the OH equivalent by the acetylation method was 240 g / eq.
The synthesis conditions and physical property values of the phenol resin compositions obtained in Synthesis Examples 1 to 9 are summarized in Table 1. In addition, content (%) of the compound of General formula (5-1) and (5-2) in a phenol resin composition is the phenol resin (namely, addition) of the chart obtained by the said number average molecular weight measuring method. It was determined from the ratio of the peak area corresponding to the compounds of the general formulas (5-1) and (5-2) in the total peak area.

Synthesis Example 10
In a glass reaction kettle equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 470.00 g (5.00 mol) of phenol, 1,4-di (methoxymethyl) benzene (hereinafter abbreviated as 1,4-PXDM). ) 276.67 g (1.67 mol) and 50% sulfuric acid aqueous solution 0.33 g were charged and reacted at 130 ° C. for 1 hour.
Thereafter, the reaction temperature was raised to 160 ° C. and the reaction was carried out for 3 hours. Meanwhile, the methanol produced was distilled off. Thereafter, the mixture was cooled to 80 ° C., and 83.44 g (1.17 mol) of 42% formalin aqueous solution was added dropwise. After the addition, the temperature was raised to 100 ° C. and the reaction was carried out for 1 hour. After completion of the reaction, washing with water was performed 3 times. The oil layer was separated, and unreacted phenol was distilled off by distillation under reduced pressure to obtain 430 g of a phenol resin.

[Manufacture of epoxy resin composition]
The epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were synthesized using the phenol resin compositions obtained in Synthesis Examples 1 to 10. About the epoxy resin composition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by the following methods.
Using gel permeation chromatography (HCL-8220 (manufactured by Tosoh Corporation), a calibration curve was created using the results of measuring standard substances under the following conditions, and the polystyrene-equivalent number average molecular weight (Mn) of each resin composition The weight average molecular weight (Mw) was determined.
column:
TSK-GEL H type G2000H × L 4 G3000H × L 1 G4000H × L 1 were connected in series and used.
Column pressure: 13.5 MPa
Solution: Tetrahydrofuran (THF)
Flow rate: 1 ml / min.
Measurement temperature: 40 ° C
Detector: Spectrophotometer (UV-8020)
RANGE: 2.56 WAVE LENGTH 254nm & RI

  Moreover, content (%) of the compound (binuclear body) of the general formula (3-1) and (3-2) in an epoxy resin composition is the epoxy of the chart obtained by the measuring method of the said number average molecular weight. It calculated | required from the ratio of the peak area corresponded to the compound of general formula (3-1) and (3-2) in the total peak area of resin (namely, what remove | excluded the additive).

Example 1
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 298.8 g (1.80 mol) of the phenol resin composition obtained in Synthesis Example 1 and 999.0 g (10.80 mol) of epichlorohydrin. ) And 93.75 g of methanol were charged and dissolved uniformly. At 50 ° C., solid 96% sodium hydroxide 75 g (1.80 mol) was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
480 g of methyl isobutyl ketone was added to the residue of the kettle and dissolved. 28.80 g (0.18 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under heating and reduced pressure to obtain 382 g of an epoxy resin composition.
The obtained epoxy resin composition had an ICI viscosity at 150 ° C. of 34 mPa · s and an epoxy equivalent of 233 g / eq. Mn and Mw of the obtained epoxy resin composition were 682 and 835, respectively.

Example 2
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 278.8 g (1.70 mol) of the phenol resin composition obtained in Synthesis Example 2 and 943.5 g (10.20 mol) of epichlorohydrin were obtained. ) And 88.54 g of methanol were charged and dissolved uniformly. At 50 ° C., 70.83 g (1.70 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
450 g of methyl isobutyl ketone was added to the residue and dissolved. 27.20 g (0.17 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under heating and reduced pressure to obtain 364 g of an epoxy resin composition.
The obtained epoxy resin composition had an ICI viscosity at 150 ° C. of 56 mPa · s and an epoxy equivalent of 239 g / eq. Mn and Mw of the obtained epoxy resin composition were 775 and 1017, respectively.

Example 3
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 290.7 g (1.70 mol) of the phenol resin composition obtained in Synthesis Example 3 and 943.5 g (10.20 mol) of epichlorohydrin. ) And 88.54 g of methanol were charged and dissolved uniformly. At 50 ° C., 70.83 g (1.70 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
450 g of methyl isobutyl ketone was added to the residue and dissolved. 27.20 g (0.17 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under heating and reduced pressure to obtain 380 g of an epoxy resin composition.
The obtained epoxy resin composition had an ICI viscosity at 150 ° C. of 64 mPa · s and an epoxy equivalent of 244 g / eq. Mn and Mw of the obtained epoxy resin composition were 873 and 1274, respectively.

Example 4
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 232.4 g (1.40 mol) of the phenol resin composition obtained in Synthesis Example 4 and 777.0 g (8.40 mol) of epichlorohydrin were obtained. ) And 72.92 g of methanol were charged and dissolved uniformly. At 50 ° C., 58.33 g (1.40 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
373g of methyl isobutyl ketone was added to the kettle residue and dissolved. A 25% aqueous sodium hydroxide solution (22.40 g, 0.14 mol) was added, and the mixture was reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under heating and reduced pressure to obtain 290 g of an epoxy resin composition.
The obtained epoxy resin composition had an ICI viscosity at 150 ° C. of 33 mPa · s and an epoxy equivalent of 233 g / eq.

Example 5
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 282 g (1.5 mol) of the phenol resin composition obtained in Synthesis Example 7, 832.5 g (9.0 mol) of epichlorohydrin, Methanol 78.13 g was charged and dissolved uniformly. At 50 ° C., 62.5 g (1.5 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
500 g of methyl isobutyl ketone was added to the residue and dissolved. 24.0 g (0.1 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under reduced pressure by heating to obtain 340 g of an epoxy resin composition.
The resulting epoxy resin composition had an ICI viscosity at 150 ° C. of 82 mPa · s and an epoxy equivalent of 250 g / eq.

Example 6
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 272 g (2.0 mol) of the phenol resin obtained in Synthesis Example 10, 1110 g of epichlorohydrin (12.0 mol), and 88.00 g of methanol. Was uniformly dissolved. At 50 ° C., 83.33 g (2.0 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
480 g of methyl isobutyl ketone was added to the residue of the kettle and dissolved. 32.0 g (0.2 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. 340 g of epoxy resin was obtained by distilling off methyl isobutyl ketone under heating and reduced pressure.

Comparative Example 1
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas inlet tube, 303.0 g (1.50 mol) of the phenol resin composition obtained in Synthesis Example 5 and 832.5 g (9.0 mol) of epichlorohydrin were obtained. ) And 78.13 g of methanol were charged and dissolved uniformly. At 50 ° C., 62.50 g (1.50 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
460 g of methyl isobutyl ketone was charged into the kettle residue and dissolved. 24.00 g (0.15 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under heating and reduced pressure to obtain 380 g of an epoxy resin composition.
The obtained epoxy resin composition had an ICI viscosity at 150 ° C. of 100 mPa · s and an epoxy equivalent of 273 g / eq. Mn and Mw of the obtained epoxy resin composition were 732 and 940, respectively.

Comparative Example 2
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 312.0 g (1.50 mol) of the phenol resin composition obtained in Synthesis Example 6 and 832.5 g (9.0 mol) of epichlorohydrin were obtained. ) And 78.13 g of methanol were charged and dissolved uniformly. At 50 ° C., 62.50 g (1.50 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
460 g of methyl isobutyl ketone was charged into the kettle residue and dissolved. 24.00 g (0.15 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under heating and reduced pressure to obtain 380 g of an epoxy resin composition.
The obtained epoxy resin composition had an ICI viscosity at 150 ° C. of 103 mPa · s and an epoxy equivalent of 276 g / eq. Mn and Mw of the obtained epoxy resin composition were 822 and 1152, respectively.

Comparative Example 3
As the epoxy resin, an epoxy resin (EOCN-1020-55: manufactured by Nippon Kayaku Co., Ltd.) obtained by epoxidizing a commercially available phenol resin synthesized from orthocresol and formalin was used.

Comparative Example 4
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 278.8 g (1.70 mol) of the phenol resin composition obtained in Synthesis Example 8 and 943.5 g (10.20 mol) of epichlorohydrin were obtained. ) And 88.54 g of methanol were charged and dissolved uniformly. At 50 ° C., 70.83 g (1.70 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
450 g of methyl isobutyl ketone was added to the residue and dissolved. 27.20 g (0.17 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. By distilling off methyl isobutyl ketone under heating and reduced pressure, 360 g of an epoxy resin composition was obtained.
The resulting epoxy resin composition had an ICI viscosity at 150 ° C. of 30 mPa · s and an epoxy equivalent of 230 g / eq.

Comparative Example 5
In a glass reaction vessel equipped with a stirrer, a condenser, and a nitrogen gas introduction tube, 240 g (1.0 mol) of the phenol resin composition obtained in Synthesis Example 9, 555 g (6.0 mol) of epichlorohydrin, and methanol 78 .13 g was charged and dissolved uniformly. At 50 ° C., 41.7 g (1.0 mol) of solid 96% sodium hydroxide was added in portions over 90 minutes. Thereafter, the reaction was carried out at 50 ° C. for 2 hours, and the reaction was continued for another 2 hours after the temperature was raised to 70 ° C. After completion of the reaction, excess epichlorohydrin was removed under reduced pressure.
500 g of methyl isobutyl ketone was added to the residue and dissolved. 16.0 g (0.1 mol) of 25% aqueous sodium hydroxide solution was added and reacted at 70 ° C. for 1 hour. After completion of the reaction, the water washing treatment was repeated 5 times until the aqueous layer became neutral. Methyl isobutyl ketone was distilled off under heating and reduced pressure to obtain 300 g of an epoxy resin composition.
The ICI viscosity at 150 ° C. of the obtained epoxy resin composition could not be measured, and the epoxy equivalent was 320 g / eq.

  Table 2 shows the physical property values of the epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5, the blending ratio of the cured product 1 of the epoxy resin composition obtained by the method shown below, and the properties of the cured product 1 Are summarized in

[Preparation of cured product 1]
Epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, and a general-purpose phenol novolac resin of HF-3M (hydroxyl equivalent: 107 g / eq) manufactured by Meiwa Kasei Co., Ltd. as a curing agent, and triphenylphosphine as a curing accelerator (Sometimes abbreviated as TPP).
Specifically, the epoxy resin composition and the curing agent are blended so that the phenol hydroxyl group equivalent ratio and the epoxy equivalent ratio are 1: 1, and the TPP catalyst is 0 with respect to the weight of the epoxy resin composition of the blending. .15 wt% was charged. These were heated to 150 ° C., melted and mixed, vacuum degassed, cast into a 150 ° C. mold (thickness 4 mm), cured at 150 ° C. for 5 hours, and then further 180 ° C. for 8 hours. A molded product was produced by curing.
The test method of various physical properties of the obtained molded body (cured product) is as described above.

[Preparation of cured product 2]
Table 3 shows the physical property values of the epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, the blending ratio of the cured product 2 of the epoxy resin composition obtained by the method shown below, and the properties of the cured product 2 Are summarized in

Epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5, HF-3M (hydroxyl equivalent: 107 g / eq) made by Meiwa Kasei Co., Ltd. as a curing agent, triphenylphosphine (TPP) as a curing accelerator In some cases, EMC (Epoxy Molding Compound) was synthesized by the following method using Tatsumori silica (MSR-2212) as a filler.
The epoxy resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 and the curing agent were blended so that the phenol hydroxyl group equivalent and the epoxy equivalent ratio were 1: 1, and the TPP catalyst was an epoxy resin composition of the blend. 2.3 wt% of the product weight was charged. The filler was added to 83 wt%, and these were kneaded with a biaxial kneader under conditions of 100 ° C to 110 ° C and pulverized to prepare EMC powder.
A tablet was prepared using the obtained EMC powder, and spiral flow measurement was performed.
Moreover, a test piece was prepared using the above-mentioned EMC powder with a transfer molding machine and post-cured at 180 ° C. for 8 hours to obtain a test piece for evaluating water absorption, strength, and flame retardancy.

In the said Table 2 and Table 3, "% / EP" shows the weight% with respect to an epoxy resin composition.
In Tables 2 and 3, the ICI viscosity at 150 ° C. of Comparative Example 5 could not be measured because the viscosity of each resin composition was too high.
The epoxy resin composition obtained in the examples of the present invention is an epoxy resin having a low melt viscosity while maintaining a high glass transition temperature, low moisture absorption, high adhesion, heat resistance, rapid curing, and flame retardancy. It became clear that it was a composition.

  ADVANTAGE OF THE INVENTION According to this invention, the hardened | cured material can provide the epoxy resin composition which has a low melt viscosity, maintaining a high glass transition temperature, low hygroscopicity, high adhesiveness, heat resistance, quick hardening, and a flame retardance.

Claims (8)

The following general formula (1):

(In the formula, R represents the following general formulas (2-1) and (2-2):

Represents at least one bridging group selected from a biphenylylene group and a xylylene group, and R ¹ , R ² and R ³ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or an aryl group, and p, q and r are each an integer of 0 to 2. M and n are positive numerical values, and G represents a glycidyl group. ), The following general formulas (3-1) and (3-2):

(In the formula, G represents a glycidyl group, and R ⁴ and R ⁵ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group). An epoxy resin composition having a compound content of 50% or less.   The epoxy resin composition according to claim 1, wherein m / n is 0.04 to 20 and the melt viscosity at 150 ° C. is 10 to 200 mPa · s.   The epoxy resin composition according to claim 1 or 2, wherein R contains at least a biphenylylene crosslinking group.   The epoxy resin composition according to claim 3, wherein the biphenylylene crosslinking group contains a 4,4′-biphenylylene crosslinking group.   Furthermore, the epoxy resin composition as described in any one of Claims 1-4 which contains a hardening | curing agent and the effect promoter as needed.   Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-5. The following general formula (4):

(In the formula, R represents the following general formulas (2-1) and (2-2):

Represents at least one bridging group selected from a biphenylylene group and a xylylene group, and R ¹ , R ² and R ³ may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or an aryl group, and p, q and r are each an integer of 0 to 2. M and n represent positive numerical values. ), The following general formulas (5-1) and (5-2):

(Wherein R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group), and the content ratio of the compound represented by 50% The method for producing an epoxy resin composition according to any one of claims 1 to 4, wherein the following phenol resin composition and epihalohydrin are reacted in the presence of an alkali metal hydroxide. The phenol resin composition is a phenol compound, formaldehyde, and the following general formulas (6-1) and (6-2):

(Wherein Y represents a halogen atom, a hydroxyl group or an alkoxyl group having 1 to 6 carbon atoms), and obtained by reacting with one or more kinds of cross-linked compounds selected from the compounds represented by A method for producing an epoxy resin composition according to claim 7