JP2008201714A - Bifunctional hydroxy compound, epoxy resin, method for producing the same, epoxy resin composition, cured product thereof and semiconductor sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition imparting excellent solder heat resistance and flame retardance to a cured product, to provide the cured product thereof, to provide a multifunctional hydroxy compound and to provide an epoxy resin. <P>SOLUTION: A bifunctional hydroxy compound has a molecular structure represented by structural formula (1) (wherein, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>4</SP>represent each a 1-4C alkyl group; and R<SP>5</SP>, R<SP>6</SP>, R<SP>7</SP>and R<SP>8</SP>represent each independently a hydrogen atom or a 1-4C alkyl group). An epoxidized material thereof is used as a principal agent or a curing agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention provides a cured product excellent in solder heat resistance because it has a high glass transition temperature, a low moisture absorption rate and a low thermal elastic modulus, and further provides flame retardancy without using a flame retardant represented by a brominated flame retardant. The present invention relates to a polyvalent hydroxy compound and an epoxy resin that give an excellent cured product, a method for producing the same, an epoxy resin composition containing these, and a cured product.

  Epoxy resins or phenol resins are widely used in the fields of electronics and high-performance paints because they give a cured product having excellent low shrinkage (dimensional stability), electrical insulation, and chemical resistance during curing. In these technical fields, technological innovation has been remarkable in recent years, and in order to respond to environmental problems such as lead-containing solder and dioxin problems, superior characteristics such as solder heat resistance and flame resistance are strongly demanded. Yes.

  As means for meeting these requirements, a polyfunctional hydroxy compound obtained by reacting 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol with a binder such as paraxylene halide An epoxy resin derived therefrom is known (see Patent Document 1).

  However, such polyfunctional hydroxy compounds or epoxy resins have a situation in which the heat resistance required in recent years cannot be ensured because the crosslink density of the resulting cured product increases and the thermal elastic modulus increases.

JP 2006-248912 A

  Therefore, the problem to be solved by the present invention is to provide an epoxy resin composition capable of imparting excellent solder heat resistance and flame retardancy to a cured product, its cured product, a polyfunctional hydroxy compound, and an epoxy resin.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor used a bifunctional hydroxy compound having a specific polynuclear structure as a curing agent for epoxy resin, or used the bifunctional hydroxy compound. Furthermore, when an epoxy resin obtained by reacting with epihalohydrin is used as a main agent, the cured product has been found to exhibit superior solder heat resistance and flame retardancy, which has been completed, and the present invention has been completed.

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

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表す。）
で表される分子構造を有することを特徴とする２官能性ヒドロキシ化合物に関する。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.)
The bifunctional hydroxy compound characterized by having the molecular structure represented by these.

  The present invention further includes the following structural formula (2):

（式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を示し、Ｘはハロゲン原子、又は、炭素原子数１〜３のアルコキシ基を表す。）
で表される化合物（ａ１）と、
下記構造式（３）

(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom or an alkoxy having 1 to 3 carbon atoms. Represents a group.)
A compound (a1) represented by:
The following structural formula (3)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表す。）
で表される化合物（ａ２）
とを反応させることを特徴とする２官能性ヒドロキシ化合物の製造法に関する。

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
A compound represented by formula (a2)
It is related with the manufacturing method of the bifunctional hydroxy compound characterized by making these react.

  The present invention further comprises an epoxy resin composition comprising an epoxy resin (A) and a curing agent for epoxy resin (B) as essential components, and the following structural formula (1) is used as the curing agent for epoxy resin (B).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表す。）
で表される分子構造を有することを特徴とする２官能性ヒドロキシ化合物を用いることを特徴とするエポキシ樹脂組成物（以下、これを「エポキシ樹脂組成物（Ｉ）」と略記する。）に関する。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.)
It is related with the epoxy resin composition (it abbreviates as "epoxy resin composition (I)" hereafter) characterized by using the bifunctional hydroxy compound characterized by having the molecular structure represented by these.

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

  The present invention further relates to a semiconductor sealing material characterized in that the epoxy resin composition (I) further contains an inorganic filler (C) in a proportion of 70 to 95% by mass in the composition.

  The present invention further includes the following structural formula (4):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表し、Ｒ^９及びＲ^１０は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜５である。）
で表される分子構造を有することを特徴とするエポキシ樹脂に関する。

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a carbon atom. It represents a C1-4 alkyl group, ^{R 9} and ^{R 10} represents a hydrogen atom or a methyl radical, n is from 0 to 5 on average of the repeating unit.)
It has the molecular structure represented by this.

  The present invention further includes the following structural formula (2):

（式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を示し、Ｘはハロゲン原子、又は、炭素原子数１〜３のアルコキシ基を表す。）
で表される化合物（ａ１）と、
下記構造式（３）

(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom or an alkoxy having 1 to 3 carbon atoms. Represents a group.)
A compound (a1) represented by:
The following structural formula (3)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表す。）
で表される化合物（ａ２）
とを反応させて下記構造式（１）

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
A compound represented by formula (a2)
And the following structural formula (1)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表す。）
で表される分子構造を有する２官能性ヒドロキシ化合物（Ａ）を得、
次いで、該化合物（Ａ）とエピハロヒドリンとを反応させることを特徴とするエポキシ樹脂の製造法に関する。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.)
A bifunctional hydroxy compound (A) having a molecular structure represented by
Then, it is related with the manufacturing method of the epoxy resin characterized by making this compound (A) and epihalohydrin react.

  The present invention further comprises an epoxy resin composition comprising an epoxy resin (A) and a curing agent for epoxy resin (B) as essential components, wherein the epoxy resin (A) has the following structural formula (4):

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表し、Ｒ^９及びＲ^１０は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜５である。）
で表される分子構造を有することを特徴とするエポキシ樹脂を用いることを特徴とするエポキシ樹脂組成物（以下、これを「エポキシ樹脂組成物（II）」と略記する。）に関する。

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a carbon atom. It represents a C1-4 alkyl group, ^{R 9} and ^{R 10} represents a hydrogen atom or a methyl radical, n is from 0 to 5 on average of the repeating unit.)
The present invention relates to an epoxy resin composition (hereinafter abbreviated as “epoxy resin composition (II)”) characterized by using an epoxy resin characterized by having a molecular structure represented by:

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

  The present invention further relates to a semiconductor sealing material characterized in that the epoxy resin composition (II) further contains an inorganic filler (C) in a proportion of 70 to 95% by mass in the composition.

  ADVANTAGE OF THE INVENTION According to this invention, the epoxy resin composition which can provide the outstanding solder | pewter heat resistance and flame retardance to hardened | cured material, its hardened | cured material, a polyfunctional hydroxy compound, and an epoxy resin can be provided.

  The bifunctional hydroxy compound of the present invention has the following structural formula (1)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表す。）
で表される分子構造を有することを特徴とするものである。
ここで、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４を構成する炭素原子数１〜４のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｔ−プロピル基を表し、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８を構成する炭素原子数１〜４のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｔ−プロピル基を表す。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.)
It has the molecular structure represented by these.
Here, the alkyl group having 1 to 4 carbon atoms constituting R ¹ , R ² , R ³ , and R ⁴ represents a methyl group, an ethyl group, an n-propyl group, a t-propyl group, and R ⁵ The alkyl group having 1 to 4 carbon atoms constituting R ⁶ , R ⁷ and R ⁸ represents a methyl group, an ethyl group, an n-propyl group or a t-propyl group.

  Specific examples of the bifunctional hydroxy compound include compounds represented by the following structural formulas x-1 to x-7.

Among these, the production is particularly easy, and in the structural formula (1) represented by x-1, x-2, x-3, and x-4, the cured product has good solder heat resistance. ^A compound in which all of ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms is preferred.

  Moreover, when using the said compound as a hardening | curing agent for epoxy resins, or an epoxy resin raw material, multiple types may be used together, In that case, it is hardening that a hydroxyl equivalent is 140-300 g / eq. It is preferable from the viewpoint that the solder heat resistance of the product is excellent.

To produce a bifunctional hydroxy compound, for example,
The following structural formula (2)

（式中、Ｘはハロゲン原子、又は、炭素原子数１〜３のアルコキシ基を表す。）
で表される化合物（ａ１）と、
下記構造式（３）

(In the formula, X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms.)
A compound (a1) represented by:
The following structural formula (3)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表す。）
で表される化合物（ａ２）
とを反応させるか、或いは、この反応によって得られた下記構造式（１’）

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
A compound represented by formula (a2)
Or the following structural formula (1 ′) obtained by this reaction:

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表す。）
で表される２官能性ヒドロキシ化合物に、アルキル化剤を反応させることによって製造することができる。
ここで下記構造式（２）

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
It can manufacture by making an alkylating agent react with the bifunctional hydroxy compound represented by these.
Here, the following structural formula (2)

（式中、Ｘはハロゲン原子、又は、炭素原子数１〜３のアルコキシ基を表す。）
で表される化合物（ａ１）としては、具体的には、オルソキシレンジクロライド、オルソキシレンジブロマイド、オルソキシレンジヒドロキサイド、オルソキシレンジメトキサイド、オルソキシレンジエトキサイド、オルソキシレンジイソプロポキサイド等が挙げられる。これらのなかでもオルソキシレンジクロライドやオルソキシレンジヒドロキサイド、オルソキシレンジメトキサイドが、反応性が良い点から好ましい。また、上記化合物（ａ１）は、反応に供する際、２種類以上を組み合わせて用いてもよい。

(In the formula, X represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms.)
Specific examples of the compound represented by formula (a1) include orthoxylene dichloride, orthoxylene dibromide, orthoxylene dihydroxide, orthoxylene dimethoxide, orthoxylene diethoxide, orthoxylene diisopropoxide Is mentioned. Of these, ortho-xylene dichloride, ortho-xylene dihydroxide, and ortho-xylene dimethoxide are preferable from the viewpoint of good reactivity. Moreover, when the said compound (a1) uses for reaction, you may use it in combination of 2 or more types.

  Next, the following structural formula (3)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表す。）
で表される化合物（ａ２）としては、具体的には、３，３’，５，５’−テトラメチル−４，４’−ビフェノール、３，３’，５，５’−テトラエチル−４，４’−ビフェノール、３，３’，５，５’−テトラプロピル−４，４’−ビフェノール、３，３’，５，５’−テトライソプロピル−４，４’−ビフェノール、３，３’，５，５’−テトラターシャリーブチル−４，４’−ビフェノール等が挙げられる。
これらのなかでも３，３’、５，５’−テトラメチル−４，４’−ビフェノールを用いた場合、難燃性と耐熱性および硬化性のバランスが良好となるため好ましい。また、上記化合物（ａ２）は、反応に供する際、２種類以上を組み合わせて用いてもよい。

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
Specifically, as the compound (a2) represented by 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetraethyl-4, 4′-biphenol, 3,3 ′, 5,5′-tetrapropyl-4,4′-biphenol, 3,3 ′, 5,5′-tetraisopropyl-4,4′-biphenol, 3,3 ′, 5,5′-tetratertiary butyl-4,4′-biphenol and the like.
Among these, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol is preferable because the balance between flame retardancy, heat resistance and curability is improved. Moreover, when the said compound (a2) uses for reaction, you may use it in combination of 2 or more types.

  When carrying out the above reaction, the reaction ratio between the compound (a1) and the compound (a2) is 1/1 / 0.5 / 1 in terms of the former / the latter molar ratio. This is preferable from the viewpoint of high purity.

  The above reaction can be carried out in the presence of an acidic catalyst or a basic catalyst. Examples of acidic catalysts that can be used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acid is mentioned. Examples of the basic catalyst include alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and calcium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate.

  Of these, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are preferable. Although the usage-amount of these catalysts is not specifically limited, It is preferable that it is the range used as 0.1-30 weight% with respect to the total mass with a raw material component. The form of these catalysts is not particularly limited, and the catalyst may be used in the form of an aqueous solution or in the form of a solid.

  The above reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent that can be used here include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged.

  The reaction temperature is usually in the range of 40 to 180 ° C, particularly 60 to 80 ° C. Moreover, reaction time is 1 to 10 hours normally. These organic solvents can be used alone or in combination of several kinds. Further, it is preferable to distill off water or alcohols produced during the reaction out of the system using a fractionating tube or the like in order to carry out the reaction quickly.

  In addition, when the resulting bifunctional hydroxy compound is highly colored, an antioxidant or a reducing agent may be added to the reaction system in order to suppress it. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. Examples of the neutralizing agent used for the neutralization treatment include basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline when an acidic catalyst is used as a reaction catalyst. On the other hand, when a basic catalyst is used as a reaction catalyst, acidic substances such as hydrochloric acid, sodium hydrogen phosphate, and oxalic acid can be used. After neutralization or washing with water, the solvent and unreacted substances are distilled off under heating under reduced pressure, and the product is concentrated to obtain the desired bifunctional hydroxy compound.
In addition, in the reaction product obtained in this way, the following structural formula (b1) as a by-product in addition to the target structural formula (1 ′).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表す。）
で表される化合物が反応生成物中に混入する。本発明では、該反応生成物中に構造式（ｂ１）で表される化合物の含有率が３０質量％以下、特に２０質量％以下であることが本発明の効果が顕著なものとなる点から好ましい。

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
Is mixed into the reaction product. In the present invention, the content of the compound represented by the structural formula (b1) in the reaction product is 30% by mass or less, particularly 20% by mass or less from the point that the effect of the present invention becomes remarkable. preferable.

In the structural formula (1), the compound having an alkyl group having 1 to 4 carbon atoms in any of R ⁵ , R ⁶ , R ⁷ and R ⁸ is represented by the following structural formula (1 ′ )

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基を表す。）
で表される２官能性ヒドロキシ化合物に、塩化アルミニウムのごときルイス酸触媒の存在下にアルキル化剤を反応させることによって得ることができる。

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
Can be obtained by reacting an alkylating agent in the presence of a Lewis acid catalyst such as aluminum chloride.

  Examples of the alkylating agent used here include those usually used as an alkylating agent in Friedel-Crafts alkylation reaction. Specific examples thereof include unsaturated aliphatic carbonization such as ethylene, acetylene, propylene and butene. Examples include hydrogen, chloromethane, bromomethane, iodomethane, fluoromethane, chloroethane, bromoethane, iodoethane, fluoroethane, halogenated hydrocarbons such as t-butyl chloride, methanol, ethanol, isopropyl alcohol, and t-butyl alcohol.

  In the reaction of the compound represented by the compound (1 ′) with an alkylating agent, the reaction product at the production of the compound (1 ′) is subjected to a reaction with the alkylating agent without purification. In the obtained reaction product, an alkylated product of the compound represented by the structural formula (1 ′), specifically, the following structural formula (b2)

で表され、かつ、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８の少なくとも１つが炭素原子数１〜４のアルキル基であって、その他が水素原子である化合物も副生成物として混入し得る。本発明では、該反応生成物中に構造式（ｂ２）で表される化合物の含有率は３０質量％以下、特に２０質量％以下であることが好ましい。

And at least one of R ⁵ , R ⁶ , R ⁷ , and R ⁸ is an alkyl group having 1 to 4 carbon atoms and the other is a hydrogen atom, may be mixed as a by-product. In the present invention, the content of the compound represented by the structural formula (b2) in the reaction product is preferably 30% by mass or less, particularly preferably 20% by mass or less.

  Next, the epoxy resin composition (I) of the present invention is an epoxy resin composition containing an epoxy resin (A) and a curing agent for epoxy resin (B) as essential components, and the curing agent for epoxy resin (B). As the bifunctional hydroxy compound (hereinafter abbreviated as “bifunctional hydroxy compound (b)”), that is, the following structural formula (1)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表す。）
で表される分子構造を有することを特徴とする２官能性ヒドロキシ化合物を用いることを特徴とするものである。かかるエポキシ樹脂組成物を硬化させた硬化物は、前記したとおり、従来になく優れたハンダ耐熱性及び難燃性を発現するものである。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜4.)
The bifunctional hydroxy compound characterized by having the molecular structure represented by these is used. As described above, a cured product obtained by curing such an epoxy resin composition exhibits excellent soldering heat resistance and flame retardancy.

The epoxy resin (A) used here is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenyl. Methane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin,
A naphthol-phenol co-condensed novolak epoxy resin, a naphthol-cresol co-condensed novolac epoxy resin, an aromatic hydrocarbon formaldehyde resin-modified phenol resin epoxy resin, a biphenyl-modified novolac epoxy resin, and the structural formula (4) And the epoxy resin of the present invention.

  Moreover, these epoxy resins may be used independently and may mix 2 or more types. Among these epoxy resins, bisphenol F type epoxy resin, biphenyl type epoxy resin, and tetramethylbiphenyl type epoxy resin are preferable because of their low viscosity, and phenol aralkyl type epoxy resin and biphenyl modified are preferable in terms of excellent flame retardancy. The novolac type epoxy resin and the epoxy resin of the present invention represented by the structural formula (4) are preferable.

  Further, in the epoxy resin composition (I) of the present invention, not only the bifunctional hydroxy compound (b) as the curing agent for epoxy resin (B), but also other curing agents as long as the characteristics of the present invention are not impaired. Can be used together. In this case, when used in combination, the proportion of the bifunctional hydroxy compound in the curing agent for all epoxy resins (B) is preferably in the range of 30% by weight or more, particularly in the range of 40% by weight or more. It is preferable.

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

Here, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative.

  Examples of the amide compounds include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.

  Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride.

Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trimethylol methane resin, tetramethylol resin Phenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin ( Polyvalent naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine modified phenolic resin (melamine, benzoguanamine, etc.) Polyhydric phenol compound phenol nucleus is connected) polyhydric phenol compounds such as and and modified products thereof.
These other curing agents may be used alone or in combination of two or more.

  Among these, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, Biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenolic resin are preferable because they are excellent in flame retardancy, especially aromatic hydrocarbon formaldehyde resin-modified phenolic resin, phenol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenolic resin, biphenyl. Modified naphthol resins, aminotriazine-modified phenol resins, and the like are particularly preferable from the viewpoint of excellent flame retardancy.

  The blending amount of the epoxy resin (A) and the epoxy resin curing agent (B) in the epoxy resin composition (I) of the present invention is not particularly limited, but mechanical properties of the resulting cured product, etc. From the point of being favorable, the quantity from which the active group in a hardening | curing agent becomes 0.7-1.5 equivalent is preferable with respect to a total of 1 equivalent of the epoxy group of an epoxy resin.

  Next, the epoxy resin of the present invention has the following structural formula (4)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、それぞれ独立に水素原子または炭素原子数１〜４のアルキル基を表し、
Ｒ^９及びＲ^１０は水素原子又はメチル基を表し、
ｎは繰り返し単位の平均で０〜５である。）
で表される分子構造を有することを特徴とするものである。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 carbon atom. Represents an alkyl group of ~ 4,
R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group,
n is 0-5 on the average of a repeating unit. )
It has the molecular structure represented by these.

Here, in the structural formula (4), as the alkyl group having 1 to 4 carbon atoms constituting R ¹ , R ² , R ³ and R ⁴ , a methyl group, an ethyl group, an n-propyl group, t- Represents a propyl group, and the alkyl group having 1 to 4 carbon atoms constituting R ⁵ , R ⁶ , R ⁷ and R ⁸ represents a methyl group, an ethyl group, an n-propyl group, or a t-propyl group.

  Examples of the repeating unit constituting the structural formula (4) include those represented by the following structural formulas e-1 to e-7.

Among these, in the structural formula (4) represented by e-1, e-2, e-3, and e-4, R is particularly easy to produce and has good solder heat resistance of the cured product. ^A compound in which all of ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms is preferred.

  In the structural formula (4), the epoxy resin can be produced by reacting the bifunctional hydroxy compound (b) with epihalohydrin.

A specific method for reacting the bifunctional hydroxy compound (b) with epihalohydrin is, for example, by adding 2 to 10 mol of epihalohydrin to 1 mol of the phenolic hydroxyl group of the bifunctional hydroxy compound (b), and adding this mixture to the mixture. While adding or gradually adding 0.9 to 2.0 mol of the basic catalyst to 1 mol of the phenolic hydroxyl group of the bifunctional hydroxy compound (b), it is 0.5 to 10 at a temperature of 20 to 120 ° C. The method of making it react for time is mentioned.
Here, the basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, an aqueous solution of a basic catalyst is continuously added, and water and epihalohydrins are continuously distilled off from the reaction mixture under reduced pressure or normal pressure, followed by liquid separation to remove water. Epihalohydrins are preferred because the method of continuously returning them to the reaction mixture and carrying out the reaction is excellent in productivity and the desired product can be obtained with high purity.

  When industrial production is performed, the first batch of epoxy resin production uses all of the prepared epihalohydrin, but after the next batch, the epihalohydrin recovered from the crude reaction product and the amount consumed in the reaction. It is preferable to use in combination with a new epihalohydrin corresponding to the amount disappeared. At this time, the epihalohydrin to be used is not particularly limited, and examples thereof include epichlorohydrin, methyl epichlorohydrin, epibromohydrin and the like. Of these, epichlorohydrin is preferable because it is easily available.

  Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are particularly preferable from the viewpoint of excellent catalytic activity for the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide, potassium hydroxide, and calcium hydroxide. These alkali metal hydroxides may be used in a solid form as described above, but are preferably used in an aqueous solution. In that case, the alkali metal hydroxide is used in an aqueous solution of about 10 to 55% by mass. Is preferable from the viewpoint of excellent workability.

  Moreover, the said reaction can raise the reaction rate in the synthesis | combination of an epoxy resin by using an organic solvent together. Examples of such an organic solvent include 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, methyl cellosolve, and ethyl cellosolve. And aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylformamide and the like, and the like, cellosolves such as tetrahydrofuran, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After performing the above reaction, the reaction product is washed with water, and unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by weight based on the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  In the reaction product thus obtained, the following structural formula (b3) is caused by a by-product contained in the raw material bifunctional hydroxy compound.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８はそれぞれ独立に水素原子または炭素原子数１〜４のアルキル基、Ｒ^９及びＲ^１０は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜５である。）
で表される分子構造を有するエポキシ樹脂が副生成物として反応生成物中に混入する。本発明では、該反応生成物中に構造式（ｂ３）で表されるエポキシ樹脂の含有率が３０質量％以下、特に２０質量％以下であることが本発明の効果が顕著なものとなる点から好ましい。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 to carbon atoms. 4 alkyl groups, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, and n is 0 to 5 on the average of the repeating units.
An epoxy resin having a molecular structure represented by the formula is mixed into the reaction product as a by-product. In the present invention, the content of the epoxy resin represented by the structural formula (b3) in the reaction product is 30% by mass or less, particularly 20% by mass or less, and the effect of the present invention becomes remarkable. To preferred.

The epoxy resin composition (II) of the present invention is an epoxy resin composition having an epoxy resin (A) and a curing agent for epoxy resin (B) as essential components, and is described in detail below as the epoxy resin (A). Structural formula (4)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は炭素原子数１〜４のアルキル基、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８はそれぞれ独立に水素原子または炭素原子数１〜４のアルキル基、Ｒ^９及びＲ^１０は水素原子又はメチル基を表し、ｎは繰り返し単位の平均で０〜５である。）
で表される分子構造を有するエポキシ樹脂（以下、これを「エポキシ樹脂（Ａ’）」と略記する。）を用いることを特徴とするものである。

(In the formula, R ¹ , R ² , R ³ , and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or 1 to carbon atoms. 4 alkyl groups, R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, and n is 0 to 5 on the average of the repeating units.
An epoxy resin having a molecular structure represented by (hereinafter, abbreviated as “epoxy resin (A ′)”) is used.

  Examples of the epoxy resin curing agent (B) used in the epoxy resin composition (II) of the present invention include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like.

Here, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative.

  Examples of the amide compounds include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.

  Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride.

Phenol compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, trimethylol methane resin, tetramethylol resin Phenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin ( Polyvalent naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine modified phenolic resin (melamine, benzoguanamine, etc.) Phenol nucleus polyhydric phenol compound linked is) a polyhydric phenol compound and modified products thereof such as, as well, such as difunctional hydroxy compounds of the present invention described above can be mentioned.
These other curing agents may be used alone or in combination of two or more.

  Among these, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, Biphenyl-modified phenolic resin, biphenyl-modified naphthol resin, and aminotriazine-modified phenolic resin are preferable because they are excellent in flame retardancy, especially aromatic hydrocarbon formaldehyde resin-modified phenolic resin, phenol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenolic resin, biphenyl. Modified naphthol resin, aminotriazine modified phenolic resin, bifunctional hydroxy compound of the present invention described above, etc. Particularly preferred from the viewpoint of excellent flame retardancy.

  The epoxy resin (A) used in the epoxy resin composition (II) of the present invention is used in combination with the epoxy resin represented by the structural formula (4) in addition to other epoxy resins as long as the effects of the present invention are not impaired. can do.

Other epoxy resins that can be used here include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, tri Phoxymethane type epoxy resin, tetraphenylethane type epoxy resin dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type poxy Resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified Novolac type epoxy resins.

  Moreover, these epoxy resins may be used independently and may mix 2 or more types. Among these epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and tetramethylbiphenyl-type epoxy resins are preferable in terms of particularly low viscosity, and phenol aralkyl-type epoxy resins and biphenyls are preferable in terms of excellent flame retardancy. A modified novolac type epoxy resin is preferred.

  The blending amount of the epoxy resin (A) and the curing agent (B) in the epoxy resin composition (II) of the present invention is not particularly limited, but the mechanical properties of the resulting cured product are good. From the point, it is preferable that the amount of the active groups in the curing agent is 0.7 to 1.5 equivalents with respect to a total of 1 equivalent of epoxy groups of the epoxy resin.

  In addition to the epoxy resin (A) and the epoxy resin curing agent (B), the epoxy resin compositions (I) and (II) detailed above can be used in combination with a curing accelerator as required. . Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  The epoxy resin compositions (I) and (II) of the present invention described above in detail have good flame retardancy of the cured product even if the epoxy resin or its curing agent is not blended with a conventionally used flame retardant. It will be something. However, in order to exert a higher degree of flame retardancy, for example, in the field of semiconductor sealing materials, it contains substantially halogen atoms in a range that does not reduce the moldability in the sealing process and the reliability of the semiconductor device. Non-halogen flame retardants that do not work may be blended.

  An epoxy resin composition containing such a non-halogen flame retardant contains substantially no halogen atom, but does not contain a halogen atom due to a trace amount of impurities of about 5000 ppm or less derived from epihalohydrin contained in the epoxy resin, for example. May be.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydro Examples thereof include cyclic organic phosphorus compounds such as oxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, curing agent, non-halogen type When using red phosphorus as a non-halogen flame retardant in 100 parts by mass of the epoxy resin composition (I) or (II) containing all of the flame retardant and other fillers and additives, 0.1-2. It is preferable to mix | blend in the range of 0 mass part, and when using an organophosphorus compound, it is preferable to mix | blend in the range of 0.1-10.0 mass part similarly, Especially 0.5-6.0 mass part It is preferable to mix in the range.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, among which triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, melam sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate and a phenol resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) or (iii) above with paulownia oil, isomerized linseed oil, etc. .

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

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 10 parts by mass in 100 parts by mass. It is particularly preferable to blend in the range of 0.1 to 5 parts by mass.

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

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone flame retardant is appropriately selected according to the type of the silicone flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 20 parts by mass. preferable. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

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

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

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

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

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

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

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, cured The epoxy resin composition (I) or (II) in which all of the agent, non-halogen flame retardant and other fillers and additives are blended may be blended in the range of 0.05 to 20 parts by mass. It is particularly preferable to blend in the range of 0.5 to 15 parts by mass.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. In the range of 0.005 to 10 parts by mass in 100 parts by mass of the epoxy resin composition (I) or (II) containing all of the epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix.

  The epoxy resin composition (I) or (II) of the present invention can be blended with an inorganic filler (C) as necessary. Examples of the inorganic filler (C) include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like for semiconductor sealing material applications, and silver powder and copper powder for conductive paste applications. Examples include conductive fillers.

  In the present invention, in particular, in addition to the epoxy resin (A) and the curing agent (B) in the epoxy resin composition (I), an inorganic filler (C) is further contained in the composition at a ratio of 70 to 95% by mass. Or, in addition to the phenol resin (B ′) and the epoxy resin (A ′) in the epoxy resin composition (II), the proportion of the inorganic filler (C) in the composition is 70 to 95% by mass. When it contains, it becomes the semiconductor sealing material of this invention.

  Here, in the semiconductor sealing material of the present invention, the amount of the inorganic filler (C) is in the range of 70 to 95% by mass of the filler per 100 parts by mass of the epoxy resin composition, as described above. Especially, in order to improve a flame retardance, moisture resistance, solder crack resistance, and to reduce a linear expansion coefficient, it is especially preferable that it is 80-95 mass%. Moreover, when containing an inorganic filler (C) in the ratio used as 80-95 mass% in a composition, it is preferable that the said inorganic filler (C) is a fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica.

  The method for producing the semiconductor encapsulating material of the present invention from the epoxy resin composition (I) or (II) comprises the above-mentioned components and further other compounding agents such as an extruder, a kneader and a roll. It is possible to use a melt-mixed epoxy resin composition by mixing thoroughly until it becomes uniform. In addition, as semiconductor package molding, the semiconductor sealing material is cast, or molded using a transfer molding machine, injection molding machine, etc., and further heated at 50 to 200 ° C. for 2 to 10 hours. A method for obtaining a certain semiconductor device is given.

  The epoxy resin composition (I) or (II) of the present invention is used for, for example, an underfill material, a conductive paste, a laminated board, an electronic circuit board, and the like in addition to the above-described semiconductor sealing material applications. It can be used for casting materials, adhesives, interlayer insulating materials for build-up substrates, coating materials such as insulating paints, and the like. Among the various uses described above, it can be suitably used for a semiconductor sealing material and an underfill material, particularly a semiconductor sealing material, which are particularly used for electronic parts.

  In order to process the epoxy resin composition (I) or (II) of the present invention into a printed circuit board composition, for example, a resin composition for prepreg can be used. Although it can be used without a solvent depending on the viscosity of the epoxy resin composition, it is preferable to obtain a resin composition for prepreg by varnishing using an organic solvent. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this epoxy resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.

  When the epoxy resin composition (I) or (II) of the present invention is used as a conductive paste, for example, fine conductive particles are dispersed in the epoxy resin composition to form an anisotropic conductive film composition. And a paste resin composition for circuit connection that is liquid at room temperature and an anisotropic conductive adhesive.

  As a method for obtaining an interlayer insulating material for a build-up substrate from the epoxy resin composition (I) or (II) of the present invention, for example, a wiring in which a circuit is formed from the curable resin composition appropriately blended with rubber, filler, etc. The substrate is applied using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  Moreover, the epoxy resin composition (I) of the present invention can be further used as a resist ink. In this case, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent (B) are blended with the epoxy resin (A), and a pigment, talc and filler are further added to form a resist. A method for forming a resist ink cured product after coating on a printed circuit board by a screen printing method after an ink composition is used.

  In the epoxy resin composition (I) or (II) of the present invention, various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier can be appropriately added according to the various uses described above. .

  The epoxy resin composition (I) or (II) of the present invention can be cured by a conventional method according to the purpose or application to be used to obtain a cured product. Under the present circumstances, the method of obtaining hardened | cured material adds the various compounding component to the epoxy resin composition (I) or (II) of this invention, and also mix | blended the composition obtained by mix | blending a hardening accelerator suitably, 20 A method of heating in a temperature range of about ˜250 ° C. is preferred. A general method of an epoxy resin composition can also be adopted as a molding method. The cured product thus obtained is useful in various applications such as laminates, cast articles, adhesive layers, coating films, and films.

  Next, the present invention will be specifically described with reference to examples and comparative examples. Hereinafter, “part” and “%” are based on weight unless otherwise specified, and the softening point, GPC measurement, NMR, and MS spectrum were measured under the following conditions.

1) GPC:
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Used polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
2) NMR: “NMR GSX270” manufactured by JEOL Ltd.
3) MS: JEOL Ltd. double convergence type weight analyzer AX505H (FD505H)

Example 1 [Synthesis of Bifunctional Hydroxy Compound (A-1)]
In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, the following formula [7]

で表される化合物１６６部、３，３’、５，５’−テトラメチル−４，４’−ビフェノール２６６部を仕込み、室温下、窒素を吹き込みながら撹拌した。メタンスルホン酸８部を発熱に注意しながら液温が８０℃を超えないようにゆっくり添加した。その後油浴中で１５０℃まで加熱し、分留管を用いて生成するメタノールを抜き出した後、更に２時間反応させた。反応終了後、５％ＮａＯＨを系内が中性になるまで加え、減圧下でメタノールを留去後、下記構造式

And 266 parts of 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol were charged and stirred at room temperature while blowing nitrogen. 8 parts of methanesulfonic acid was added slowly so as not to exceed 80 ° C. while paying attention to heat generation. Thereafter, the mixture was heated to 150 ° C. in an oil bath, and methanol produced was extracted using a fractionating tube, followed by further reaction for 2 hours. After completion of the reaction, 5% NaOH was added until the inside of the system became neutral, and methanol was distilled off under reduced pressure.

で表される本発明の２官能性ヒドロキシ化合物（Ａ−１）３７０部を得た。得られた２官能性ヒドロキシ化合物の水酸基当量は１８７ｇ／ｅｑ（理論値１７２ｇ／ｅｑ）であった。マススペクトルを測定したところ、主成分の分子量は式[８]に相当するＭ＋＝３４４であり、ＧＰＣよりその純度は７６％であることが確認された。ＧＰＣチャートを図１に、ＴＯＦ−ＭＳスペクトルチャートを図２に示す。

370 parts of the bifunctional hydroxy compound (A-1) represented by the present invention was obtained. The obtained bifunctional hydroxy compound had a hydroxyl equivalent of 187 g / eq (theoretical value: 172 g / eq). When the mass spectrum was measured, the molecular weight of the main component was M + = 344 corresponding to the formula [8], and it was confirmed by GPC that the purity was 76%. A GPC chart is shown in FIG. 1, and a TOF-MS spectrum chart is shown in FIG.

Example 2 [Synthesis of Epoxy Resin (B-1)]
187 parts of the bifunctional hydroxy compound (A-1) obtained in Example 1 and 463 g of epichlorohydrin (5.0 mol) while purging nitrogen gas purge to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer ), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. Then, 510 g of methyl isobutyl ketone and 170 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the following structural formula.

で表される本発明のエポキシ樹脂（Ｂ−１）２５０部を得た。得られたエポキシ樹脂のエポキシ当量は２５０ｇ／ｅｑであり、エポキシ当量から算出したｎは０．１であった。

The epoxy resin (B-1) 250 part of this invention represented by these was obtained. The epoxy equivalent of the obtained epoxy resin was 250 g / eq, and n calculated from the epoxy equivalent was 0.1.

Example 3 [Synthesis of Epoxy Resin (B-2)]
In Example 2, 200 parts of epoxy resin (B-2) was obtained in the same manner as in Example 2 except that 93 g of epichlorohydrin was used instead of 463 g of epichlorohydrin. The epoxy equivalent of the obtained epoxy resin was 831 g / eq, and n calculated from the epoxy equivalent was 3.0.

Comparative Example 1 [Synthesis of Polyvalent Hydroxy Compound (A′-1)]
In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, the following formula [9]

で表される化合物１６６部、３，３’、５，５’−テトラメチル−４，４’−ビフェノール２６６部を仕込み、室温下、窒素を吹き込みながら撹拌した。メタンスルホン酸８部を発熱に注意しながら液温が８０℃を超えないようにゆっくり添加した。その後油浴中で１５０℃まで加熱し、分留管を用いて生成するメタノールを抜き出した後、更に２時間反応させた。反応終了後、５％ＮａＯＨを系内が中性になるまで加え、減圧下でメタノールを留去後、下記構造式

And 266 parts of 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol were charged and stirred at room temperature while blowing nitrogen. 8 parts of methanesulfonic acid was added slowly so as not to exceed 80 ° C. while paying attention to heat generation. Thereafter, the mixture was heated to 150 ° C. in an oil bath, and methanol produced was extracted using a fractionating tube, followed by further reaction for 2 hours. After completion of the reaction, 5% NaOH was added until the inside of the system became neutral, and methanol was distilled off under reduced pressure.

（式中、ｎの平均値は２．７である。）で表される多価ヒドロキシ化合物（Ａ’−１）３７０部を得た。得られた多価ヒドロキシ化合物の水酸基当量は１６２ｇ／ｅｑ（理論値１５８ｇ／ｅｑ）であった。マススペクトルを測定したところ、ｎ＝１、ｎ＝２、ｎ＝３、 ｎ＝４にそれぞれ相当するＭ＋＝５８７、９３１、１２７６、１６２０ が確認された。ＧＰＣより未反応の３，３’、５，５’−テトラメチル−４，４’−ビフェノールは８％であることが確認された。ＧＰＣチャートを図３に示す。

(In the formula, the average value of n is 2.7.) 370 parts of a polyvalent hydroxy compound (A′-1) represented by the following formula was obtained. The polyvalent hydroxy compound obtained had a hydroxyl group equivalent of 162 g / eq (theoretical value: 158 g / eq). When the mass spectrum was measured, M + = 587, 931, 1276, and 1620 corresponding to n = 1, n = 2, n = 3, and n = 4 were confirmed. GPC confirmed that the unreacted 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol was 8%. A GPC chart is shown in FIG.

Comparative Example 2 [Synthesis of Epoxy Resin (B′-1)]
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 162 parts of the polyvalent hydroxy compound (A′-1) obtained in Example 1 and 463 g of epichlorohydrin (5.0 mol) were added. ), 139 g of n-butanol and 2 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 g (1.1 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. During this time, the distillate distilled by azeotropic distillation was separated with a Dean-Stark trap, the water layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. Then, 510 g of methyl isobutyl ketone and 170 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with water 150 g was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain the following structural formula.

で表されるエポキシ樹脂（Ｂ’−１）２１０部を得た。得られたエポキシ樹脂のエポキシ当量は２６５ｇ／ｅｑであった。

210 parts of epoxy resin (B′-1) represented by The epoxy equivalent of the obtained epoxy resin was 265 g / eq.

Comparative Example 3 [Synthesis of Polyvalent Hydroxy Compound (A′-2)]
In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, the following formula [9]

で表される化合物１６６部、３，３’、５，５’−テトラメチル−４，４’−ビフェノール４８４部、２−メトキシエタノール５００部を仕込み、室温下、窒素を吹き込みながら撹拌した。メタンスルホン酸１４部を発熱に注意しながら液温が８０℃を超えないようにゆっくり添加した。その後油浴中で１５０℃まで加熱し、分留管を用いて生成するメタノールおよび２−メトキシエタノールを抜き出した後、更に２時間反応させた。反応終了後、５％ＮａＯＨを系内が中性になるまで加え、減圧下で２−メトキシエタノールを留去後、下記構造式

166 parts of a compound represented by the formula: 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol 484 parts and 2-methoxyethanol 500 parts were added and stirred at room temperature while blowing nitrogen. 14 parts of methanesulfonic acid was slowly added so as not to exceed 80 ° C. while paying attention to heat generation. Thereafter, the mixture was heated to 150 ° C. in an oil bath, and methanol and 2-methoxyethanol produced were extracted using a fractionating tube, and then further reacted for 2 hours. After completion of the reaction, 5% NaOH was added until the system became neutral, and 2-methoxyethanol was distilled off under reduced pressure.

（式中、ｎの平均値は１．１である。）で表される多価ヒドロキシ化合物（Ａ’−２）６１５部を得た。得られた多価ヒドロキシ化合物の水酸基当量は１５１ｇ／ｅｑ（理論値１４７ｇ／ｅｑ）であった。マススペクトルを測定したところ、ｎ＝１、ｎ＝２、ｎ＝３、 ｎ＝４にそれぞれ相当するＭ＋＝５８７、９３１、１２７６、１６２０ が確認された。ＧＰＣより未反応の３，３’、５，５’−テトラメチル−４，４’−ビフェノールは１３％であることが確認された。ＧＰＣチャートを図４に示す。

(In the formula, the average value of n is 1.1.) 615 parts of a polyvalent hydroxy compound (A′-2) represented by the following formula was obtained. The obtained polyvalent hydroxy compound had a hydroxyl group equivalent of 151 g / eq (theoretical value: 147 g / eq). When the mass spectrum was measured, M + = 587, 931, 1276, and 1620 corresponding to n = 1, n = 2, n = 3, and n = 4 were confirmed. From GPC, it was confirmed that unreacted 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol was 13%. A GPC chart is shown in FIG.

Comparative Example 4 [Synthesis of Epoxy Resin (B′-2)]
In Comparative Example 2, an epoxy resin (B′-2) was obtained in the same manner as Comparative Example 2 except that 151 parts of the polyvalent hydroxy compound (A′-2) was used instead of the polyvalent hydroxy compound (A′-1). 200 parts were obtained. The epoxy equivalent of the obtained epoxy resin was 245 g / eq.

Synthesis Example 1 [Synthesis of Epoxy Resin (B′-3)]
In Comparative Example 2, 176 parts of phenol alaskill resin ("Mirex XLC-LL" manufactured by Mitsui Chemicals, hydroxyl equivalent 176 g / eq, softening point 79 ° C) is used instead of the polyvalent hydroxy compound (A'-1). Otherwise, in the same manner as in Comparative Example 2, 225 parts of an epoxy resin (B′-3) was obtained. The epoxy equivalent of the obtained epoxy resin was 255 g / eq.

Examples 4-6 and Comparative Examples 5-9
Various epoxy resins and curing agents shown in Table 1, triphenylphosphine (TPP) as a curing accelerator, spherical silica (“S-COL” manufactured by Micron Co., Ltd.) as an inorganic filler, and γ-as a silane coupling agent Formulation shown in Table 1 using glycidoxytriethoxyxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.), carnauba wax (“PEARL WAX No. 1-P” manufactured by Celalica Noda Co., Ltd.), and carbon black According to the above, the desired epoxy resin composition was obtained by melt-kneading for 10 minutes at a temperature of 100 ° C. using two rolls.

  The obtained epoxy resin composition was press-molded at 180 ° C. for 10 minutes, and then further cured at 180 ° C. for 5 hours, and then a 1.6 mm-thick test piece according to the UL-94 test method was prepared. The physical properties of the cured product were confirmed by each of the evaluation test methods. The results are also shown in Table 1.

  Moisture absorption rate (%): The weight increase rate after treatment for 300 hours under the condition of 85 ° C./85% RH was determined.

  Glass transition temperature: Measured with a viscoelasticity measuring device (solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., double currant lever method; frequency 1 Hz, heating rate 3 ° C./min).

  Flame retardancy: Based on the UL-94 test method, a flame test was performed using five test pieces having a thickness of 1.6 mm.

Solder heat resistance: The test piece is left in an atmosphere of 85 ° C. and 85% RH for 72 hours, and after moisture absorption treatment, it is immersed in a solder bath at 260 ° C. for 10 seconds, and the crack generation rate at that time is examined. It was. The number of test pieces is 50.

In the table, “YX-4000H” is a tetramethylbiphenol type epoxy resin (“YX-4000H”, epoxy equivalent 195 g / eq) manufactured by Japan Epoxy Resin Co., Ltd., and “XLC-LL” is manufactured by Mitsui Chemicals, Inc. Phenol aralkyl resin (“Mirex XLC-LL”, hydroxyl group equivalent 176 g / eq, softening point 79 ° C.).
As is clear from the above evaluation results, the epoxy resin composition using the epoxy resin curing agent and the epoxy resin of the present invention is more resistant to heat than the similar compound using paraxylene dimethoxide as a raw material. Excellent solder heat resistance and flame retardancy.

1 is a GPC chart of the bifunctional hydroxy compound obtained in Example 1. FIG. FIG. 2 is a TOF-MS spectrum of the bifunctional hydroxy compound obtained in Example 1. FIG. 3 is a GPC chart of the polyvalent hydroxy compound obtained in Comparative Example 1. FIG. 4 is a GPC chart of the polyvalent hydroxy compound obtained in Comparative Example 3.

Claims (14)

The following structural formula (1)

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a carbon atom. Represents an alkyl group of formulas 1 to 4.)
The bifunctional hydroxy compound characterized by having the molecular structure represented by these. The bifunctional hydroxy compound according to claim 1, wherein the hydroxyl equivalent is in the range of 140 to 300 g / equivalent.

The following structural formula (3)

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
A compound represented by formula (a2)
And a method for producing a bifunctional hydroxy compound. The following structural formula (2)

(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom or an alkoxy having 1 to 3 carbon atoms. Represents a group.)
A compound (a1) represented by:
The following structural formula (3)

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms.)
A compound represented by formula (a2)
The method according to claim 3, wherein the alkylating agent is reacted. The production method according to claim 3 or 4, wherein a reaction ratio between the compound (a1) and the compound (a2) is a ratio of 1/1 to 0.5 / 1 in terms of a molar ratio of the former / the latter. An epoxy resin composition comprising an epoxy resin (A) and an epoxy resin curing agent (B) as essential components, wherein the epoxy resin curing agent (B) is a bifunctional hydroxy compound according to claim 1 or 2. An epoxy resin composition characterized by using. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 6. A semiconductor sealing material, wherein the epoxy resin composition according to claim 6 further contains an inorganic filler (C) in a proportion of 70 to 95% by mass in the composition. The following structural formula (4)

(Wherein R ¹ , R ² , R ³ , and R ⁴ represent an alkyl group having 1 to 4 carbon atoms, and R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom or a carbon atom. It represents a C1-4 alkyl group, ^{R 9} and ^{R 10} represents a hydrogen atom or a methyl radical, n is from 0 to 5 on average of the repeating unit.)
An epoxy resin having a molecular structure represented by: The epoxy resin according to claim 8, wherein the epoxy equivalent is in the range of 240 to 1500 g / equivalent. A method for producing an epoxy resin, comprising reacting an epihalohydrin with the bifunctional hydroxy compound (A) obtained by the production method according to claim 3 or 4. An epoxy resin composition comprising an epoxy resin (A) and an epoxy resin curing agent (B) as essential components, wherein the epoxy resin according to claim 9 or 10 is used as the epoxy resin (A). Epoxy resin composition. A cured product obtained by curing the epoxy resin composition according to claim 11. The epoxy resin composition according to claim 12, further comprising an inorganic filler (C) in a proportion of 70 to 95% by mass in the composition.

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