JP2015127397A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition comprising a polyvalent glycidyl compound and a specific phenolic curing agent, making it possible to obtain a cured product having excellent heat resistance.SOLUTION: A curable resin composition comprises a polyvalent glycidyl compound (A) having a glycidyl group and a glycidyl ether group binding to an identical aromatic ring in a molecule, and a phenolic curing agent (B) having no substituent at an ortho position of a phenolic hydroxyl group.

Description

  The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition that includes a polyvalent glycidyl compound (hereinafter, may be referred to as an epoxy compound or an epoxy resin) that is excellent in heat resistance, electrical characteristics, and the like and that is particularly suitable for the field of electronic materials.

  Glycidyl compounds (epoxy resins) are excellent in electrical properties, adhesiveness, heat resistance and the like, and are used in many applications such as the paint field, civil engineering field, and electrical field. In particular, aromatic glycidyl compounds represented by bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin, etc. are water resistant, adhesive, mechanical properties, heat resistance, It excels in electrical insulation and economy, and is widely used in combination with various curing agents.

  The glycidyl compound is molecularly designed to meet the target physical properties in order to improve the physical properties of the cured product using the glycidyl compound. In addition to the structural design of the glycidyl compound skeleton itself, the molecular design includes consideration of combinations with curing agents and the like. For example, in phenol novolac type epoxy resins, by adjusting the polymerization degree, molecular weight distribution, etc. of the glycidyl compound, the fluidity at the time of thermosetting is changed, or the heat resistance, adhesiveness, etc. of the cured product are controlled. be able to.

  As one aspect regarding molecular design, a polyvalent glycidyl compound having three or more glycidyl groups in one molecule is compared with a glycidyl compound having two or less glycidyl groups in one molecule. It is known that heat resistance is improved. This is because the number of reactive functional groups contained per molecule increases, so that the number of crosslinking points per unit volume in the cured product of the composition containing the glycidyl compound and, if necessary, the curing agent increases. This is because the micromotion of the is controlled. In addition, increasing the density of glycidyl groups in the composition increases the polar sites such as hydroxyl groups in the cured product, which improves adhesion between adherends such as metals and inorganic materials and the cured product. It has been.

  Examples of a method for obtaining a glycidyl compound having a high functional group density in the molecule include a method of introducing two or more glycidyl groups into the aromatic ring skeleton of a compound having an aromatic ring. Examples of such a compound include a polyvalent glycidyl ether compound having two or more glycidyl ether groups in one aromatic ring, a compound having a glycidyl group in the ortho position or para position with respect to the glycidyl ether group bonded to the phenol moiety. It is done. The glycidyl ether group includes a glycidyl group because it is a combination of a glycidyl group and an oxygen atom.

  As a polyvalent glycidyl compound having a glycidyl group in the ortho position or para position with respect to the glycidyl ether group bonded to the phenol moiety, for example, a compound having bisphenol F as a basic skeleton in Patent Document 1 (Japanese Patent Laid-Open No. 63-142019). Is disclosed.

  However, the polyvalent glycidyl compounds having a glycidyl group at the ortho-position or para-position with respect to the glycidyl ether group bonded to the phenol moiety disclosed so far all relate to bisphenol compounds or biphenyl compounds typified by bisphenol F. Is. Further, the physical properties of the curable resin composition containing these polyvalent glycidyl compounds are not described in detail.

Japanese Patent Laid-Open No. 63-142019

  An object of the present invention is to provide a curable resin composition containing a polyvalent glycidyl compound and a specific phenol-based curing agent from which a cured product having excellent heat resistance is obtained.

  The inventors have excellent heat resistance by curing a polyvalent glycidyl compound having a glycidyl group and a glycidyl ether group bonded to the same aromatic ring in the molecule as a substrate in combination with a specific phenolic curing agent. It was found that a cured product was obtained. That is, the present invention includes the following embodiments.

（式中、Ｒ^１及びＲ^２は、各々独立して、下記式（２）又は（３）で表される基であり、Ｑは、各々独立して、式：−ＣＲ^３Ｒ^４−で表されるアルキレン基、炭素数３〜１２のシクロアルキレン基、炭素数６〜１０の単独芳香環からなるアリーレン基若しくは２〜３の炭素数６〜１０の芳香環が結合してなるアリーレン基、炭素数７〜１２の二価の脂環式縮合環、又はこれらを組み合わせた二価基であり、Ｒ^３及びＲ^４は各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数３〜１２のシクロアルキル基、又は炭素数６〜１０のアリール基であり、ｎは０〜５０の整数を表す。）

（式（２）中のＲ^５、Ｒ^６及びＲ^７は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表し、式（３）中のＲ^８、Ｒ^９及びＲ^１０は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表す。）
［３］前記多価グリシジル化合物（Ａ）が、ビスフェノール−Ａ、ビスフェノール−Ｆ、フェノールノボラック、トリフェニルメタンフェノール、ビフェニルアラルキル型フェノール、フェニルアラルキル型フェノール、又は無置換のテトラヒドロジシクロペンタジエン骨格のフェノール若しくは両端に−ＣＨ_２−が結合した無置換のテトラヒドロジシクロペンタジエン骨格のフェノールのいずれかの基本骨格を有し、ＯＲ^１に対してＲ^２がオルト位又はパラ位に位置するグリシジル化合物である［２］に記載の硬化性樹脂組成物。
［４］前記フェノール系硬化剤（Ｂ）がフェノールノボラック樹脂、フェノールアラルキル樹脂、ナフトールアラルキル樹脂、ジシクロペンタジエン／フェノール重合型樹脂、ベンズアルデヒド／フェノール重合型ノボラック樹脂、又はテルペン／フェノール重合型樹脂のいずれかである［１］〜［３］のいずれかに記載の硬化性樹脂組成物。
［５］前記フェノール系硬化剤（Ｂ）がフェノールノボラック樹脂である［４］に記載の硬化性樹脂組成物。
［６］前記多価グリシジル化合物（Ａ）におけるグリシジル基及びグリシジルエーテル基の合計に対する前記フェノール系硬化剤（Ｂ）における水酸基のモル比率（フェノール系硬化剤（Ｂ）の水酸基のモル数／［多価グリシジル化合物（Ａ）のグリシジル基及びグリシジルエーテル基の合計モル数］）が０．８〜１．０である［１］〜［５］のいずれかに記載の硬化性樹脂組成物。
［７］硬化促進剤（Ｃ）をさらに含む［１］〜［６］のいずれかに記載の硬化性樹脂組成物。
［８］充填材（Ｄ）をさらに含む［１］〜［７］のいずれかに記載の硬化性樹脂組成物。
［９］前記充填材（Ｄ）が非晶質シリカ、結晶性シリカ、アルミナ、窒化ホウ素、窒化アルミニウム、窒化ケイ素、及びそれらの混合物からなる群より選択される無機充填材である、［８］に記載の硬化性樹脂組成物。
［１０］半導体封止用である［９］に記載の硬化性樹脂組成物。 [1] A polyvalent glycidyl compound (A) having a glycidyl group and a glycidyl ether group bonded to the same aromatic ring in the molecule, a phenol-based curing agent (B) having no substituent at the ortho position of the phenolic hydroxyl group, A curable resin composition comprising:
[2] The polyvalent glycidyl compound (A) is a compound represented by the general formula (1), wherein the epoxy equivalent of the compound is E, the skeleton of the compound has all R ¹ and R ² are represented by the formula The curable resin composition according to [1], wherein E / Er is 1.01-1.60, when Er is the theoretical epoxy equivalent of the compound represented by (3).

(Wherein, R ¹ and R ² are each independently a group represented by the following formula (2) or (3), and Q are each independently represented by the formula: —CR ³ R ⁴ —. An alkylene group, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group composed of a single aromatic ring having 6 to 10 carbon atoms, or an arylene group formed by bonding an aromatic ring having 2 to 3 carbon atoms and 6 to 10 carbon atoms, A divalent alicyclic condensed ring having 7 to 12 carbon atoms, or a divalent group obtained by combining these, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carbon An alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 to 50.)

(In formula (2), R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an alkyl group having 6 to 10 carbon atoms. Represents an aryl group, and R ⁸ , R ⁹ and R ¹⁰ in formula (3) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a carbon number. Represents 6 to 10 aryl groups.)
[3] The polyvalent glycidyl compound (A) is bisphenol-A, bisphenol-F, phenol novolak, triphenylmethanephenol, biphenylaralkyl type phenol, phenylaralkyl type phenol, or phenol having an unsubstituted tetrahydrodicyclopentadiene skeleton. Alternatively, it is a glycidyl compound having any basic skeleton of an unsubstituted tetrahydrodicyclopentadiene skeleton having —CH ₂ — bonded to both ends, wherein R ² is located in the ortho or para position with respect to OR ¹ . Curable resin composition as described in [2].
[4] The phenolic curing agent (B) is any of phenol novolak resin, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene / phenol polymerization resin, benzaldehyde / phenol polymerization novolak resin, or terpene / phenol polymerization resin. The curable resin composition according to any one of [1] to [3].
[5] The curable resin composition according to [4], wherein the phenol-based curing agent (B) is a phenol novolac resin.
[6] The molar ratio of hydroxyl groups in the phenolic curing agent (B) to the total of glycidyl groups and glycidyl ether groups in the polyvalent glycidyl compound (A) (number of moles of hydroxyl groups in the phenolic curing agent (B) / [multiple The curable resin composition according to any one of [1] to [5], wherein the total number of moles of glycidyl group and glycidyl ether group of the valent glycidyl compound (A)] is 0.8 to 1.0.
[7] The curable resin composition according to any one of [1] to [6], further including a curing accelerator (C).
[8] The curable resin composition according to any one of [1] to [7], further including a filler (D).
[9] The filler (D) is an inorganic filler selected from the group consisting of amorphous silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, and mixtures thereof. [8] The curable resin composition described in 1.
[10] The curable resin composition according to [9], which is for semiconductor encapsulation.

  By using a curable resin composition in which the polyvalent glycidyl compound of the present invention and a specific phenolic curing agent are used in combination, the crosslinking density in the resin can be increased, and the heat resistance, rigidity, adhesiveness, etc. are excellent. A cured product can be obtained. Therefore, the curable resin composition of the present invention can be suitably used for semiconductor encapsulants, particularly power semiconductor encapsulants that require high heat resistance.

2 is a ¹ H-NMR spectrum of a product obtained in Synthesis Example 2. 2 is a ¹ H-NMR spectrum of a product obtained in Synthesis Example 4. ¹ is a ¹ H-NMR spectrum of a product obtained in Synthesis Example 6. It is a figure which shows the fitting with the cure reaction rate calculated | required by measuring the heat_generation | fever behavior of the curable resin composition of Example 1 using DSC, and a Kamal model numerical formula (1).

  Hereinafter, the present invention will be described in detail. The curable resin composition of the present invention includes a polyvalent glycidyl compound (A) having a glycidyl group and a glycidyl ether group bonded to the same aromatic ring in the molecule, and a phenol having no substituent at the ortho position of the phenolic hydroxyl group. And a system curing agent (B). In the present specification, the “glycidyl group” means a substituted or unsubstituted glycidyl group, and the “glycidyl ether group” means a substituted or unsubstituted glycidyl ether group.

式中、Ｒ^１及びＲ^２は、各々独立して、下記式（２）又は（３）で表される基であり、Ｑは、各々独立して、式：−ＣＲ^３Ｒ^４−で表されるアルキレン基、炭素数３〜１２のシクロアルキレン基、炭素数６〜１０の単独芳香環からなるアリーレン基若しくは２〜３の炭素数６〜１０の芳香環が結合してなるアリーレン基（例えば、２つの芳香環が結合してなるアリーレン基としてビフェニル骨格を有するアリーレン基が、３つの芳香環が結合してなるアリーレン基としてトリフェニル骨格を有するアリーレン基が挙げられる）、炭素数７〜１２の二価の脂環式縮合環、又はこれらを組み合わせた二価基であり、Ｒ^３及びＲ^４は各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数３〜１２のシクロアルキル基、又は炭素数６〜１０のアリール基であり、ｎは０〜５０の整数を表す。

式（２）中のＲ^５、Ｒ^６及びＲ^７は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表し、式（３）中のＲ^８、Ｒ^９及びＲ^１０は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表す。式（２）及び式（３）中の＊は、酸素原子又は芳香環を構成する炭素原子との結合部であることを意味する。 [Multivalent glycidyl compound (A)]
The polyvalent glycidyl compound (A) used in the curable resin composition of the present invention has at least one aromatic ring having both a glycidyl group and a glycidyl ether group bonded in the molecule. Specifically, the compound represented by General formula (1) is mentioned.

In the formula, R ¹ and R ² are each independently a group represented by the following formula (2) or (3), and Q are each independently represented by the formula: —CR ³ R ⁴ —. An alkylene group, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group having a single aromatic ring having 6 to 10 carbon atoms, or an arylene group formed by bonding an aromatic ring having 2 to 3 carbon atoms and 6 to 10 carbon atoms (for example, An arylene group having a biphenyl skeleton as an arylene group formed by bonding two aromatic rings, and an arylene group having a triphenyl skeleton as an arylene group formed by combining three aromatic rings). A divalent alicyclic fused ring, or a divalent group obtained by combining these, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group having 2 to 10 carbon atoms. Alkenyl group, 3 to 12 carbon atoms Black alkyl group or an aryl group having a carbon number of 6 to 10, n is an integer of 0 to 50.

R ⁵ , R ⁶ and R ^{7 in} formula (2) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl having 6 to 10 carbon atoms. R ⁸ , R ⁹ and R ¹⁰ in formula (3) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or 6 carbon atoms. Represents 10 to 10 aryl groups. * In Formula (2) and Formula (3) means that it is a bond part with the carbon atom which comprises an oxygen atom or an aromatic ring.

The curable resin composition includes a compound represented by the general formula (1), the epoxy equivalent of the compound is E, and all R ¹ and R ² having the skeleton of the compound are represented by the formula (3). When the theoretical epoxy equivalent of the compound as a group is Er, E / Er is preferably 1.01-1.60. In this specification, “epoxy equivalent” means a numerical value obtained by dividing the molecular weight of a glycidyl compound by the number of oxirane rings in the molecule, and is determined by a method of measuring an epoxy equivalent described later. When the epoxy equivalent ratio (E / Er) is greater than 1.60, when used in a curable resin composition, the glass transition temperature (Tg), which is an index of heat resistance of the cured product, and mechanical properties are reduced. The curing rate of the curable resin composition may be adversely affected. A more preferable epoxy equivalent ratio (E / Er) is 1.40 or less, and further preferably 1.20 or less. In order to make the epoxy equivalent ratio (E / Er) smaller than 1.01, it takes time for purification. Therefore, in consideration of productivity, the epoxy equivalent ratio (E / Er) is more preferably 1.02 or more. Preferably it is 1.03 or more.

As an example, in the compound represented by the general formula (1) contained in the curable resin composition, n is 1, and R ¹ and R ² in the repeating unit are allyl groups (R ^{5 to} R in the formula (2)). ⁷ is all a hydrogen atom), R ¹ and R ² at both ends are both glycidyl groups, (R ^{8 to} R ¹⁰ in formula (3) are all hydrogen atoms), and Q is a methylene group. epoxy equivalent corresponds to E of, n is 1, R ¹ and R ² and R ¹ and R ² are all glycidyl groups at both ends in the repeating unit, Q is epoxy equivalent theoretical epoxy equivalent weight of the compound is a methylene group Er It corresponds to. Compound represented by the general formula (1) contained in the curable resin composition, n is 1, R ¹ and R ² and R ¹ and R ² are all glycidyl groups at both ends in the repeating unit, Q is a methylene group E / Er is 1 for a compound that is With the manufacturing method of the polyglycidyl compounds which will be described later more (wherein the R ¹ and R ² in the reaction product of the general formula (1) having the same basic skeleton (2) or formula ( In general, the product includes a compound having a different number of groups represented by 3). In that case, the epoxy equivalent E becomes an epoxy equivalent as a whole mixture of plural kinds of compounds.

As the compound represented by the general formula (1), preferable examples of R ¹ and R ² include a group represented by the formula (2) or the formula (3) in which R ^{5 to} R ¹⁰ are all hydrogen atoms. As preferable examples of Q, as an alkylene group represented by the formula: —CR ³ R ⁴ —, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or The thing which is a naphthyl group is mentioned. Preferred examples of the cycloalkylene group having 3 to 12 carbon atoms include a cyclohexylidene group, an arylene group consisting of a single aromatic ring having 6 to 10 carbon atoms, or an aromatic ring having 2 to 3 carbon atoms and 6 to 10 carbon atoms. Preferable examples of the arylene group include a phenylene group and a biphenyldiyl group. Preferable examples of the divalent alicyclic condensed ring having 7 to 12 carbon atoms include a divalent tetrahydrodicyclopentadiene ring. Preferred examples of the divalent group in which these are combined include a —CH ₂ —Ph—Ph—CH ₂ — group (in this specification, Ph means an unsubstituted benzene ring), and —CH ₂ —Ph—CH. ₂ -groups are mentioned. Preferred specific compounds include bisphenol-A, bisphenol-F, phenol novolac, triphenylmethanephenol, such as a biphenylaralkyl type phenol having a —CH ₂ —Ph—Ph—CH ₂ — skeleton, such as —CH ₂ —Ph. A basic skeleton of either a phenylaralkyl-type phenol having a —CH ₂ — skeleton, a phenol having an unsubstituted tetrahydrodicyclopentadiene skeleton, or a phenol having an unsubstituted tetrahydrodicyclopentadiene skeleton having —CH ₂ — bonded to both ends. And a glycidyl compound in which R ² is located at the ortho-position or para-position relative to OR ¹ is simpler and more preferred for production.

[Method for producing polyvalent glycidyl compound]
Next, the manufacturing method of the said polyvalent glycidyl compound (A) used for the curable resin composition of this invention is demonstrated. There is no restriction | limiting in particular in the manufacturing method of the polyvalent glycidyl compound of this invention, A well-known method can be used. As a preferable method, a 2-alkenyl group and a carbon-carbon double bond of a 2-alkenyl ether group of a compound having a 2-alkenyl group and a 2-alkenyl ether group or a glycidyl ether group bonded to the same aromatic ring are bonded. It can be obtained by oxidizing (glycidylation) using an aqueous hydrogen oxide solution as an oxidizing agent in the presence of tungstic acid, a quaternary ammonium salt, and at least two acids including at least phosphoric acid.

式中、Ｒ^１１は、各々独立して、下記式（５）又は（６）で表される基であり、Ｒ^１２は式（５）で表される基である。Ｑは、式：−ＣＲ^１３Ｒ^１４−で表されるアルキレン基、炭素数３〜１２のシクロアルキレン基、炭素数６〜１０の単独芳香環からなるアリーレン基若しくは２〜３の炭素数６〜１０の芳香環が結合してなるアリーレン基、炭素数７〜１２の二価の脂環式縮合環、又はこれらを組み合わせた二価基であり、Ｒ^１３及びＲ^１４は各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基、炭素数３〜１２のシクロアルキル基、又は炭素数６〜１０のアリール基であり、ｍは０〜５０の整数を表す。

式（５）中のＲ^１５、Ｒ^１６及びＲ^１７は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表し、式（６）中のＲ^１８、Ｒ^１９及びＲ^２０は、各々独立して、水素原子、炭素数１〜１０のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数６〜１０のアリール基を表す。式（５）及び式（６）中の＊は、酸素原子又は芳香環を構成する炭素原子との結合部であることを意味する。 The reaction substrate used in the oxidation reaction is not particularly limited as long as it is a compound having a 2-alkenyl group and a 2-alkenyl ether group or a glycidyl ether group bonded to the same aromatic ring in the molecule. A compound in which a 2-alkenyl group is located at the ortho-position or para-position with respect to the group or glycidyl ether group is preferable in that it can be obtained relatively easily. For example, a suitable 2-alkenyl compound includes a compound represented by the following general formula (4).

In the formula, each R ¹¹ is independently a group represented by the following formula (5) or (6), and R ¹² is a group represented by the formula (5). Q is an alkylene group represented by the formula: —CR ¹³ R ¹⁴ —, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group consisting of a single aromatic ring having 6 to 10 carbon atoms, or 2 to 3 carbon atoms having 6 to 6 carbon atoms. An arylene group formed by bonding 10 aromatic rings, a divalent alicyclic condensed ring having 7 to 12 carbon atoms, or a divalent group obtained by combining these, R ¹³ and R ¹⁴ are each independently hydrogen; An atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and m is an integer of 0 to 50. Represent.

R ¹⁵ , R ¹⁶ and R ^{17 in} formula (5) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl having 6 to 10 carbon atoms. R ¹⁸ , R ¹⁹ and R ²⁰ in formula (6) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 6 carbon atoms. Represents 10 to 10 aryl groups. * In Formula (5) and Formula (6) means that it is a coupling | bond part with the carbon atom which comprises an oxygen atom or an aromatic ring.

Specific examples of the 2-alkenyl compound represented by the general formula (4) include bisphenol-A, bisphenol-F, phenol novolac, triphenylmethanephenol, biphenylaralkyl type phenol, phenylaralkyl type phenol, or unsubstituted. It has a basic skeleton of either a tetrahydrodicyclopentadiene skeleton phenol or an unsubstituted tetrahydrodicyclopentadiene skeleton phenol having —CH ₂ — bonded to both ends, and R ² is in the ortho or para position relative to OR ¹ . 2-alkenyl compounds located at.

  As an example, bisphenol compounds such as 4,4′-dihydroxydiphenyldimethylmethane (bisphenol-A) and 4,4′-dihydroxydiphenylmethane (bisphenol-F), and known polyphenols such as novolak based on phenol and formaldehyde are used. Then, after converting this to the corresponding 2-alkenyl ether compound, it is derivatized to a phenol compound through a Claisen rearrangement to obtain a compound in which the 2-alkenyl group is located at the ortho-position or para-position of the phenolic hydroxyl group. be able to. By converting this phenol compound into the corresponding 2-alkenyl ether compound or glycidyl ether compound again, the compound represented by the general formula (4) can be obtained.

  As a conversion step to the 2-alkenyl ether compound after the Claisen rearrangement, for example, a method using a metal catalyst using allyl carboxylate as an allylating agent described in US Pat. No. 5,578,740 is known. In addition, J.A. Muzart et al., J. MoI. Organomet. Chem. , 326, pp. C23-C28 (1987) and the like disclose a method for converting to an allyl ether form using a metal catalyst. By these methods, a 2-alkenyl ether compound having a 2-alkenyl group at the ortho-position or para-position as a raw material for the polyvalent glycidyl compound can be obtained. Examples of the allyl etherification reaction of phenol having 2-alkenyl ortho position include a method using allyl acetate, allyl alcohol, allyl carbonate, allyl carbamate, allyl chloride, etc. as an allylating agent. It is preferable to use allyl acetate or allyl alcohol. On the other hand, the conversion to the glycidyl ether compound after the Claisen rearrangement can be performed by reacting a phenolic hydroxyl group with an epihalohydrin.

  In the case of 2-alkenyl etherification or glycidyl etherification, it is preferable to avoid the use of halogenated 2-alkenyl or epihalohydrin when it is necessary to reduce the chlorine content in the product. By avoiding these uses, halogen contamination derived from halogenated 2-alkenyl or epihalohydrin can be suppressed. According to this embodiment, when the curable resin composition is used in the field of electrical / electronic materials, an effect of improving electrical characteristics such as long-term insulation can be expected.

  In the method for producing the polyvalent glycidyl compound, the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound represented by the formula (4) as the reaction substrate is converted into an aqueous hydrogen peroxide solution. Is oxidized (glycidylated) using as an oxidizing agent. The concentration of the aqueous hydrogen peroxide solution is not particularly limited, but is generally selected from the range of about 1 to about 80% by mass, preferably about 20 to about 60% by mass. From the viewpoint of industrial productivity and the energy cost of separation, a high concentration of the aqueous hydrogen peroxide solution is preferable. On the other hand, an excessively high concentration and / or an excessive amount of the aqueous hydrogen peroxide solution is required. It is preferable not to use it from the viewpoints of economy and safety.

  The total amount of hydrogen peroxide aqueous solution used is 1.0 to 5.0 equivalents, preferably 1.1 to the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the reaction substrate. It is -3.0 equivalent, More preferably, it is 1.2-2.0 equivalent. If it is less than 1.0 equivalent, all the carbon-carbon double bonds of 2-alkenyl group and 2-alkenyl ether group cannot theoretically be oxidized. When the amount is more than 5.0 equivalents, a large amount of a reducing agent is required to quench the excess oxidizing agent, and the post-treatment process becomes complicated. The hydrogen peroxide concentration in the reaction solution decreases as the reaction proceeds. It is preferable to keep the hydrogen peroxide concentration in the reaction solution within the range of about 0.1 to about 30% by mass, more preferably about 5 to about 10% by mass by supplementing and supplementing this decrease. When the amount is less than 0.1% by mass, the productivity is deteriorated. On the other hand, when the amount is more than 30% by mass, the explosive property in the mixed composition of the solvent and water may be increased and may be dangerous.

  The hydrogen peroxide aqueous solution is added to the reaction solution in the range of 0.1 to 2 hours from the start of the addition, preferably in the range of 0.5 to 1.5 hours. If the addition time of the aqueous hydrogen peroxide solution is long (addition rate is slow), the concentration of hydrogen peroxide in the system is lowered, the efficiency of the oxidation reaction is lowered, and hydrolysis may occur in competition. In addition, if a large amount of aqueous hydrogen peroxide solution is added to the reaction solution at the beginning of the reaction at a time, the reaction may suddenly proceed and may be dangerous. It is preferable to add by adding dropwise while confirming that it is consumed in the reaction.

  It is preferable to continue the reaction even after the addition of the aqueous hydrogen peroxide solution. The reaction is preferably continued while stirring the reaction solution, and it is preferable to use a stirrer having a magnetic stirring bar or stirring blade for stirring. The stirring speed is generally in the range of 100 to 2000 rpm, and preferably in the range of 300 to 1500 rpm. The reaction liquid is a two-phase system of a 2-alkenyl compound as a reaction substrate or an organic phase containing a 2-alkenyl compound dissolved in an organic solvent and an aqueous phase containing hydrogen peroxide. It is preferable to stir so that it becomes like. As the oxidation (glycidylation) reaction of the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group proceeds, a glycidyl compound is generated, and the viscosity of the reaction solution increases. In order to prevent hydrolysis of the glycidyl group of the glycidyl compound, which is the intermediate product or the final product, and by-product formation of a gel-like product resulting therefrom, the reaction is continued for 2 to 6 hours after the addition of the hydrogen peroxide solution. After that, stirring and heating are stopped to complete the oxidation reaction. When the reaction is stopped in less than 2 hours, many carbon-carbon double bonds of the 2-alkenyl group and 2-alkenyl ether group of the reaction substrate remain, and the yield of the target product is low. When the reaction is continued for longer than 6 hours, the hydrolyzate becomes the main product, and in some cases, a gel-like product is formed. Therefore, the post-treatment step of the reaction solution becomes complicated, and the yield of the target product is reduced.

  Oxidation (glycidylation) using an aqueous hydrogen peroxide solution can be performed in the presence of a tungsten compound, a quaternary ammonium salt and a catalyst containing at least two acids including at least phosphoric acid. Since these compounds are relatively inexpensive, oxidation of carbon-carbon double bonds of 2-alkenyl groups and 2-alkenyl ether groups of 2-alkenyl compounds using hydrogen peroxide as an oxidizing agent should be performed at low cost. Can do.

  As the tungsten compound used as the catalyst, a compound that generates a tungstate anion in water is suitable, for example, tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, phosphotungstic acid, ammonium tungstate, potassium tungstate. Monohydrate and dihydrate, sodium tungstate monohydrate and dihydrate, etc., including tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate monohydrate and dihydrate A thing etc. are preferable. These tungsten compounds may be used alone or in combination of two or more.

  The catalytic activity of these compounds that produce tungstate anions in water is higher when about 0.2 to about 0.8 mole of counter cation is present per mole of tungstate anion. As a method for preparing such a tungsten composition, for example, an alkali metal salt of tungstic acid and tungstic acid may be mixed so that the tungstate anion and counter cation are in the above ratio, or tungstic acid may be mixed with an alkali compound ( Mixed with alkali metal or alkaline earth metal hydroxides, carbonates, etc.) or combined with alkali metal or alkaline earth metal salts of tungstic acid and acidic compounds such as mineral acids such as phosphoric acid and sulfuric acid Also good. Specific examples of these include a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound.

  The amount of the tungsten compound used as the catalyst is about 0.0001 to about about 0.011 to about 2 to the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound which is the reaction substrate. It is selected from the range of 20 mol%, preferably from about 0.01 to about 20 mol%.

  As the quaternary ammonium salt used as a catalyst, a quaternary organic ammonium salt having a total of 6 to 50, preferably 10 to 40, carbon atoms of the substituents bonded to the nitrogen atom is oxidized (glycidylated). The reaction activity is high and preferable.

  Quaternary ammonium salts include trioctylmethylammonium chloride, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, tricaprylmethylammonium chloride, dichloride chloride. Chlorides such as decyldimethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride; trioctylmethylammonium bromide, trioctylethylammonium bromide, dilauryldimethylammonium bromide, lauryltrimethylammonium bromide, Stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium bromide, bromide Bromides such as licaprylmethylammonium, didecyldimethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide; trioctylmethylammonium iodide, trioctylethylammonium iodide, diiodide iodide Lauryldimethylammonium, lauryltrimethylammonium iodide, stearyltrimethylammonium iodide, lauryldimethylbenzylammonium iodide, tricaprylmethylammonium iodide, didecyldimethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium iodide, iodine Iodides such as benzyltriethylammonium iodide; trioctylmethylammonium hydrogen phosphate, hydrogen phosphate Trioctylethylammonium phosphate, dilauryldimethylammonium phosphate, lauryltrimethylammonium phosphate, stearyltrimethylammonium phosphate, lauryldimethylbenzylammonium phosphate, tricaprylmethylammonium phosphate, phosphoric acid Hydrogenated didecyldimethylammonium phosphate, tetrabutylammonium phosphate hydrogenated, benzyltrimethylammonium phosphate, benzyltriethylammonium phosphate hydrogenated phosphates; trioctylmethylammonium sulfate, trioctyl hydrogenate sulfate Ethyl ammonium, dilauryl dimethyl ammonium hydrogen sulfate, lauryl trimethyl ammonium hydrogen sulfate, stearyl trimethyl ammonium hydrogen sulfate, aqueous sulfuric acid Hydrogenated sulfates such as lauryl dimethylbenzylammonium sulfate, tricaprylmethylammonium sulfate, didecyldimethylammonium sulfate, tetrabutylammonium sulfate, benzyltrimethylammonium sulfate, benzyltriethylammonium sulfate, etc. Can be mentioned.

  These quaternary ammonium salts may be used alone or in combination of two or more. The amount used is preferably about 0.0001 to about 10 mol%, more preferably about 0.000, based on the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound of the reaction substrate. It is selected from the range of 01 to about 10 mol%.

  When a phase transfer catalyst having a chloride ion, bromide ion or iodide ion as a counter anion is used as the quaternary ammonium salt, the halide content in the product increases. In order to reduce impurities derived from halogen in the product, a quaternary ammonium salt remover disclosed in JP 2010-70480 A can be used. Although it is possible to carry out the oxidation reaction using a halogen-based quaternary ammonium salt, a step of removing the quaternary ammonium salt is required, and the operation becomes complicated. For this reason, it is preferable to use a hydrogen phosphate or hydrogen sulfate as the quaternary ammonium salt, and it is more preferable to use a hydrogen sulfate.

  In the method for producing a polyvalent glycidyl compound of the present invention, phosphoric acid is used as a promoter. Phosphoric acid generates an active species by coordinating an oxygen atom to a tungsten metal center that is a catalytic metal. Moreover, pH of a reaction liquid is controlled to 1.0-4.0 by using acids other than phosphoric acid together. The pH of the reaction solution is preferably 1.2 to 3.8, and more preferably 1.4 to 3.5. When the pH of the reaction solution is higher than 4.0, the reaction rate is lowered and thus the productivity is lowered. On the other hand, when the pH is lower than 1.0, hydrolysis of the glycidyl group proceeds and the yield tends to be lowered. The amount of phosphoric acid used is preferably from about 0.1 to about 10 mol%, more preferably from about 0.1 to about 10 mol% based on the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound of the reaction substrate. It is selected from the range of 1 to about 10 mol%.

  As the acid other than phosphoric acid, either a mineral acid or an organic acid can be used. Examples of mineral acids include polyphosphoric acid, pyrophosphoric acid, sulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, and boric acid. Examples of organic acids include benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid. The amount used is preferably about 0.001 to about 10 mol%, more preferably about 0.001 mol% with respect to the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound of the reaction substrate. It is selected from the range of 01 to about 10 mol%. Among these acids, sulfuric acid is preferable because of its large buffering effect and easy pH retention in the range of 1.0 to 4.0.

  In the glycidylation reaction by oxidation, the aqueous solution of hydrogen peroxide and the above-mentioned catalyst are mixed without using an organic solvent or if necessary using an organic solvent, and the glycidylation reaction of the 2-alkenyl compound of the reaction substrate is advanced. be able to. When a solvent is used, the reaction rate becomes slow, and depending on the solvent, an undesirable reaction such as a hydrolysis reaction may easily proceed, so it is necessary to select appropriately. When the viscosity of the 2-alkenyl compound represented by the formula (4) of the reaction substrate is too high or is a solid, a minimum necessary organic solvent may be used. The organic solvent that can be used is preferably an aromatic hydrocarbon, an aliphatic hydrocarbon, or an alicyclic hydrocarbon, and examples thereof include toluene, xylene, hexane, octane, and cyclohexane. Regarding the concentration, it is advantageous in terms of production cost to keep the minimum necessary use, and the amount of the organic solvent used is preferably about 300 parts by mass or less, more preferably 100 parts by mass or less relative to 100 parts by mass of the 2-alkenyl compound. About 100 parts by mass or less.

  In addition, considering that industrial production is stable in the oxidation (glycidylation) reaction, the catalyst and the substrate are charged into the reactor first, and the reaction temperature is kept as constant as possible while the hydrogen peroxide solution is reacted. It is better to add gradually while confirming that it is consumed. By adopting such a method, even if hydrogen peroxide is abnormally decomposed in the reactor and oxygen gas is generated, the amount of hydrogen peroxide accumulated is small and the pressure rise can be minimized.

  If the reaction temperature is too high, there will be many side reactions, and if it is too low, the consumption rate of hydrogen peroxide will slow down and may accumulate in the reaction solution, so the reaction temperature is preferably about 40 to about 100 ° C. More preferably, the temperature is controlled in the range of about 50 ° C to about 80 ° C. It is preferable to perform both the addition of the aqueous hydrogen peroxide solution and the reaction after the end of the addition within the above temperature range.

  After completion of the reaction, there may be almost no difference in specific gravity between the aqueous layer and the organic layer. Two-layer separation can be carried out without using. In particular, since the specific gravity of the tungsten compound is heavy, in order to bring the aqueous layer to the lower layer, a tungsten compound exceeding the above-mentioned usage amount that is originally necessary as a catalyst may be used. In this case, it is preferable to increase the utilization efficiency of the tungsten compound by reusing the tungsten compound from the aqueous layer.

  Conversely, depending on the substrate, the specific gravity of the organic layer may be close to 1.2. In such a case, water is added to bring the specific gravity of the aqueous layer closer to 1, so that It is also possible to bring an organic layer under the layer. The extraction of the reaction solution can also be carried out using an organic solvent such as toluene, cyclohexane, hexane, methylene chloride, etc., and an optimal separation method can be selected according to the situation.

After concentrating the organic layer separated from the aqueous layer in this way, or concentrating as necessary, the polyvalent glycidyl compound obtained is taken out by a usual method such as distillation, chromatographic separation, recrystallization, sublimation, etc. Can do. The polyvalent glycidyl compound has a plurality of types represented by the general formula (1) having the same basic skeleton (the number of groups represented by the formula (2) or the formula (3) is different as R ¹ and R ² ). It is obtained as a mixture which usually contains the compound. This mixture can be separated into each compound by a known separation method as required, but can also be applied to the curable resin composition of the present invention as it is.

[Phenolic curing agent (B)]
In the curable resin composition of the present invention, a curing agent for curing the polyvalent glycidyl compound (mixture) (A) is used in combination. The curing agent used in the curable resin composition of the present invention is a phenolic curing agent having no substituent at the ortho position of the phenolic hydroxyl group.

  As the polyhydric glycidyl compound (A), the glycidyl group and the glycidyl ether group are bonded to the same aromatic ring, and the steric distance between the reaction points is close, so that the phenolic curing agent used in the curable resin composition of the present invention In addition, those having no substituent at the ortho position of the phenolic hydroxyl group are used. When a curing agent having a substituent at the ortho position of the phenolic hydroxyl group is used, the reactivity is lowered due to high steric hindrance, and the heat resistance of the cured product is lowered.

  Specific phenolic curing agents include polyphenols such as phenol novolac resin, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene / phenol polymerization resin, benzaldehyde / phenol polymerization novolak resin, terpene / phenol polymerization resin, etc. Compounds are exemplified, and among these, phenol novolac resins having particularly low steric hindrance near the phenolic hydroxyl group are preferred. Compared with these phenolic curing agents, the use of a phenolic curing agent such as a cresol novolak resin having a substituent, for example, a methyl group, at the ortho position of the phenolic hydroxyl group at the reactive site causes reactivity due to high steric hindrance. Decreases. As will be described later, this shows a tendency opposite to that when a general phenol novolac glycidyl compound in which one glycidyl ether group is bonded to one aromatic ring as a glycidyl compound is used in combination with a phenolic curing agent. . In addition, in a phenol novolac resin or the like, a site bonded to a unit having an adjacent aromatic ring may be bonded to the ortho position with respect to the phenol hydroxyl group, but this site is the ortho position of the phenolic hydroxyl group in the present specification. It does not correspond to the substituent of. In the present specification, the substituent at the ortho position of the phenolic hydroxyl group means a group bonded to only one of the aromatic rings constituting the basic skeleton, such as a methyl group of a cresol novolak resin.

  The compounding amount of the phenolic curing agent (B) is the molar ratio of the hydroxyl group of the phenolic curing agent (B) to the total of the glycidyl group and glycidyl ether group of the polyvalent glycidyl compound (mixture) (A) (phenolic curing agent). (B) The number of moles of hydroxyl group / [total number of moles of glycidyl group and glycidyl ether group of polyvalent glycidyl compound (A)] is preferably in the range of 0.8 to 1.0. The molar ratio is more preferably about 0.85 to about 0.99, and still more preferably about 0.90 to about 0.98. When the molar ratio is less than 0.8, a large number of unreacted glycidyl groups and glycidyl ether groups remain after curing, and the heat resistance of the cured product is lowered. On the other hand, when the total of the glycidyl group and glycidyl ether group of the polyvalent glycidyl compound (A) is stoichiometrically small with respect to the hydroxyl group of the phenol-based curing agent (B), that is, when the molar ratio exceeds 1.0, There exists a tendency for Tg of hardened | cured material to become low.

[Curing accelerator (C)]
It is preferable that the curable resin composition of the present invention further contains a curing accelerator (C) from the viewpoint of improving the curing rate of the composition. The curing accelerator is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; tertiary such as 1,8-diazabicyclo (5,4,0) undecene-7 Amines and salts thereof; phosphines such as triphenylphosphine and tricyclohexylphosphine; phosphonium salts such as tetrabutylphosphonium O, O-diethylphosphorodithioate, tetraphenylphosphonium thiocyanate and triphenylphosphonium bromide; aminotriazoles; octylic acid Examples thereof include tin compounds such as tin and dibutyltin dilaurate; zinc compounds such as zinc octylate; metal catalysts such as acetylacetonate complexes such as aluminum, chromium, cobalt, and zirconium. These hardening accelerators may be used independently and may use 2 or more types together.

  Although the compounding quantity of the said hardening accelerator is not specifically limited, It is 0.01-5 mass parts normally with respect to 100 mass parts of hardening components of curable resin composition. If the blending amount is less than 0.01 parts by mass, the effect of adding the above-mentioned curing accelerator tends to be not obtained, and if it exceeds 5 parts by mass, the cured product is colored, deteriorated in heat resistance, light resistance and the like. May occur. A more preferable range of the blending amount is 0.05 to 1.5 parts by mass.

  The “curing component of the curable resin composition” in the present specification contributes to curing that is added as necessary in addition to the polyvalent glycidyl compound (mixture) (A) and the phenolic curing agent (B). Other components, for example, an epoxy compound other than the polyvalent glycidyl compound (A) may be included. That is, “100 parts by mass of the curable component of the curable resin composition” means that the total amount of components contributing to curing in the curable resin composition is 100 parts by mass.

[Filler (D)]
You may mix | blend a filler with the curable resin composition of this invention. The type of filler is appropriately selected depending on the application. For example, when using the curable resin composition of this invention for a semiconductor sealing use, in order to reduce the thermal expansion coefficient of hardened | cured material, the insulating inorganic filler is mix | blended. This inorganic filler is not specifically limited, A well-known thing can be used.

Specific examples of the inorganic filler include particles of amorphous silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, and the like. From the viewpoint of reducing the viscosity, true spherical amorphous silica is particularly desirable. The inorganic filler may be subjected to surface treatment with a silane coupling agent or the like, but may not be subjected to surface treatment. These inorganic fillers have an average particle size of 0.1 to 20 μm, and a maximum particle size of 75 μm or less, particularly preferably 20 μm or less. When the average particle size is in this range, the viscosity of the curable resin composition does not become excessively high, and the injection property of the composition into narrow pitch wiring portions, narrow gap portions, etc. is also appropriate. In the present specification, the “average particle size” is a volume cumulative particle size D ₅₀ measured by a laser diffraction scattering type particle size distribution measuring device, and the “maximum particle size” is a diameter, an ellipse if the particles are spherical. The shape is the long diameter, the needle is the long axis dimension, the polygon is the longest side (triangle) or the longest diagonal (square or more), and the other is the maximum dimension. Content of the inorganic filler in curable resin composition can be suitably determined according to a use. For example, in semiconductor sealing applications, the content of the inorganic filler in the curable resin composition is generally 50 to 95% by mass, preferably 65 to 90% by mass.

[Other ingredients]
The curable resin composition of the present invention may contain a coupling agent for imparting adhesion. The coupling agent is not particularly limited. For example, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N- Examples thereof include silane coupling agents such as phenyl-3-aminopropyltrimethoxysilane. These coupling agents may be used independently and 2 or more types may be used together.

  The compounding amount of the coupling agent is usually 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin composition. When the amount is less than 0.1 parts by mass, the compounding effect of the coupling agent may not be sufficiently exhibited. When the amount exceeds 5 parts by mass, the excess coupling agent volatilizes and the curable resin composition is cured. In addition, film loss may occur.

  The curable resin composition of the present invention may contain an antioxidant in order to improve the heat resistance of the cured product of the composition. The antioxidant is not particularly limited. For example, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4 '-Butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) Phenolic antioxidants such as triphenyl phosphite, tridecyl phosphite, nonyl diphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene, 9,10-dihydro-9 -Phosphorous antioxidants such as oxa-10-phosphaphenanthrene-10-oxide; dilauryl-3,3'-thio Sulfur-based antioxidants such as dipropionate, ditridecyl-3,3′-thiodipropionate, [4,4′-thiobis (3-methyl-6-tert-butylphenyl)] bis (alkylthiopropionate); iron And metal antioxidants such as zinc and nickel. These antioxidants may be used alone or in combination of two or more.

  The compounding quantity of the said antioxidant is 0.001-2 mass parts normally with respect to 100 mass parts of curable resin compositions. When the amount is less than 0.001 part by mass, the effect of blending the antioxidant may not be sufficiently exhibited. When the amount exceeds 2 parts by mass, the antioxidant is volatilized and the curable resin composition is cured. In addition, film loss may occur, and the cured product may become brittle.

  The curable resin composition of the present invention may contain fine silica powder, high molecular weight silicone resin and the like in order to adjust the viscosity. In particular, silica fine powder is more preferable because it functions not only as a thickening action but also as a thixotropic agent, so that the fluidity of the curable resin composition of the present invention can be controlled.

  Although the average particle diameter of the said silica fine powder is not specifically limited, A preferable range is 0.1-100 nm, and a more preferable range is 1-50 nm. When used for sealing an optical semiconductor such as an LED, if it exceeds 100 nm, the transparency of the curable resin composition may decrease. On the other hand, the transparency of the curable resin composition is not a problem in applications that do not transmit light such as wiring boards such as build-up boards and semiconductor sealing such as underfills.

  The curable resin composition of the present invention may contain other additives such as an antifoaming agent, a colorant, a phosphor, a modifier, a leveling agent, a light diffusing agent, and a flame retardant as necessary.

  The method for preparing the curable resin composition of the present invention is not particularly limited, and each component is charged into a mixer such as a pot mill, a three-roll mill, a rotary mixer, a twin screw mixer, etc. at a predetermined blending ratio and mixed. Can be prepared.

  The organic solvent may be mixed as necessary at the time of preparation, and after mixing until uniform, the solvent may be volatilized. The organic solvent used in this case can be appropriately selected according to the solubility of the organic components (polyvalent glycidyl compound, phenolic curing agent, curing accelerator, etc.) in the resin composition, but acetone and toluene are easy to remove. , THF, ethyl acetate and the like are preferably used. Strongly acidic substances such as acetic acid and basic substances such as triethylamine and pyridine react with glycidyl groups or reactive hydroxyl groups, and are not preferable. Those having a high boiling point, such as dimethylformamide and dimethyl sulfoxide, are not preferable because of the remaining solvent. When a solvent is used, it is preferable to finally remove the solvent under reduced pressure to obtain a curable resin composition.

  When pulverizing the curable resin composition, there is no particular designation as long as the resin is not melted by the heat generated in the working process, but it is easy to use an agate mortar if the amount is small. When a commercially available pulverizer is used, one that generates heat during pulverization is not preferable because melting of the mixture occurs. The particle size of the powder is preferably about 1 mm or less.

  The curable resin composition of the present invention can be thermally cured. The thermosetting conditions are usually 150 to 250 ° C. Curing does not proceed sufficiently at temperatures lower than 150 ° C, and problems such as decomposition of the target product and volatilization of low molecular weight components occur at temperatures higher than 250 ° C, as well as demands on equipment used for curing. It becomes severe. The heating time for curing can be in the range of 0.5 to 48 hours. This heating may be performed in a plurality of times. In particular, when a high degree of curing is required, it is not preferable to cure at an excessively high temperature. For example, it is preferable to gradually increase the temperature to advance the curing so that the final curing temperature is 200 ° C. or lower. Preferably it is 180 degrees C or less.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Synthesis Example 1: Synthesis of Substrate (4,4 ′-(Dimethylmethylene) bis [2- (2-propenyl) phenyldiallyl ether]) In a 500 mL three-necked round bottom flask, 138 g of potassium carbonate (manufactured by Nippon Soda Co., Ltd.) 0.004 mol) dissolved in 125 g of pure water, 4,4 ′-(dimethylmethylene) bis [2- (2-propenyl) phenol] represented by formula (7) (produced by Daiwa Kasei Co., Ltd.) 80.6 g (262 mmol) and 52.0 g (0.500 mol, as a solid) of sodium carbonate (manufactured by Kanto Chemical Co., Inc.) were charged, and the reactor was purged with nitrogen gas and heated to 85 ° C. Under a nitrogen gas stream, allyl acetate (made by Showa Denko KK) 220 g (2.19 mol), triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 2.62 g (10.0 mmol), and 50% water content 5% -Pd / C-STD type (manufactured by N.E. Chemcat Co., Ltd.) 84.6 mg (0.0200 mmol as Pd atomic weight) was added, heated to 105 ° C. in a nitrogen gas atmosphere, reacted for 4 hours, then allyl acetate 22. 0 g (0.219 mol) was added and heating was continued for 12 hours. After completion of the reaction, the reaction system was cooled to room temperature, and pure water was added until all the precipitated salts were dissolved, followed by liquid separation treatment. The organic layer was separated and the organic solvent (70 ° C., 50 mmHg, 2 hours) was distilled off. After adding pure water (200 g), 200 g of toluene was added and maintained at a temperature of about 80 ° C., and it was confirmed that no white precipitate was deposited, and then Pd / C was filtered (a membrane filter having a pore diameter of 1 micron) (Pressurization (0.3 MPa) using KST-142-JA manufactured by Advantech Co., Ltd.) The filter cake was washed with 100 g of toluene and the aqueous layer was separated, and the organic layer was washed with 200 g of water at about 50 ° C. The organic layer was separated, concentrated under reduced pressure, and 4,4 ′-(dimethylmethylene) bis [2 represented by the formula (8). A brown liquid (93.6 g, 241 mmol, 92.0% yield) having a main component of-(2-propenyl) phenyl diallyl ether] was obtained, and the brown liquid was subjected to ¹ H-NMR measurement. ) Object measurement data attributable to the compound represented by was confirmed to contain as a main component. Equation (8) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 1.66 (6H, s, CH ₃ ), δ 3.39 (4H, d, PhC H ₂ CH═CH ₂ ), δ 4.95-5.55 _{(4H, m, PhCH 2 CH} = C H 2), δ5.25 (2H, d, PhOCH 2 CH = C H H), δ5.42 (2H, d, PhOCH 2 CH = CH H), δ5.25 _{(4H, m, PhOCH 2 C} H = CH 2, PhCH 2 C H = CH 2), δ6.73 (d, 2H, aromatic), δ6.90-7.08 (m, 2H, aromatic), δ7. 13-7.40 (2H, m, aromatic).

Synthesis Example 2: Synthesis of 2,2-bis (3-glycidyl-4-glycidyloxyphenyl) propane (abbreviated as BATG) Into a 200 mL three-neck round bottom flask, 4,4 ′-(dimethyl Methylene) bis [2- (2-propenyl) phenyldiallyl ether] 18.1 g (46.5 mmol), sodium tungstate monohydrate (manufactured by Nippon Inorganic Chemical Co., Ltd.) 1.53 g (4.70 mmol), phosphorus Acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.231 g (2.35 mmol), sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.230 g (2.35 mmol), and trioctylmethylammonium hydrogen sulfate (MTOAHS, Asahi) 2.17 g (4.70 mmol) manufactured by Chemical Industry Co., Ltd. was added and dissolved in 18 g of toluene (manufactured by Pure Chemical Co., Ltd.). After the temperature was raised to 65 ° C., 51.1 g (0.465 mol) of a 35% by mass hydrogen peroxide aqueous solution (manufactured by Hishie Kasei Co., Ltd.) was added dropwise over 1 hour with stirring, and the mixture was further stirred at 70 ° C. for 2 hours (stirring). Speed 400 rpm). At the initial stage of the reaction, the pH of the reaction solution was 1.5, and the pH of the reaction solution after 2 hours of reaction was 3.7. After completion of the reaction, the reaction solution was cooled to room temperature, and then 20 g of water was added to carry out a liquid separation treatment. The organic layer was separated, and the remaining hydrogen peroxide was reduced by adding and washing 15 g of an aqueous sodium sulfite solution (10% by mass, manufactured by Wako Pure Chemical Industries, Ltd.). The aqueous layer was removed, and 20 g of water was added and washed again. By isolating the organic layer and distilling off the organic solvent (toluene), 18.6 g (41) of a product having an epoxy equivalent ratio (E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of the epoxy compound of 1.05 0.0 mmol, epoxy equivalent 119, yield 88.2%). The yield was calculated as (acquired amount of the mixture containing the target epoxy compound after the post-treatment / substance amount obtained when the oxidation reaction proceeded at a reaction rate of 100%) × 100). The epoxy equivalent of the product is close to the theoretical epoxy equivalent of the compound represented by the formula (9), which suggests that the product contains almost no hydrolyzate of glycidyl group. As a result of ¹ H-NMR measurement of this product, it was confirmed that the compound represented by the formula (9) was contained as a main component. Measurement data belonging to the compound represented by the formula (9) is as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 1.64 (6H, s, CH ₃ ), δ 2.54 (2H, m, PhCH ₂ CHC H HO), δ 2.7-2.8 (6H) , M, PhC H ₂ CHCHHO, PhCH ₂ CHCH H ₂ O), δ 2.90 (4H, m, PhOC H ₂ CHCH ₂ O), δ 3.17 (2H, m, PhOCH ₂ CHC H HO), δ 3.35 ( _{2H, m, PhOCH 2 CHCH H} O), δ3.95 (2H, m, PhCH 2 C H CH 2 O), δ4.24 (2H, dd, PhOCH 2 C H CH 2 O), δ6.74 (d , 2H, aromatic), δ 7.02-7.05 (m, 4H, aromatic).

Synthesis Example 3 Synthesis of Substrate (Phenol Novolac Type Allyl Ether (Alleviated as BRG-556-AL2) Having an Allyl Group at Ortho- or Para-Position) To a 2000 mL 3-necked flask, potassium carbonate (manufactured by Nippon Soda Co., Ltd.) A solution obtained by dissolving 171.1 g (1.24 mol) in 155.6 g of pure water, phenol novolak represented by formula (10) (Shonol (registered trademark) BRG-556, o = 2 to 7) (Showa Denko Co., Ltd.) Company) 500.0 g and sodium carbonate (manufactured by Kanto Chemical Co., Inc.) 65.61 g (0.619 mol, as solid) were charged, and the reactor was purged with nitrogen gas and heated to 85 ° C. Under a nitrogen gas stream, Allyl acetate (made by Showa Denko KK) 272.7 g (2.72 mol), triphenylphosphine (made by Hokuko Chemical Co., Ltd.) 3.247 g (1) 2.4 mmol) and 50% water content 5% -Pd / C-STD type (manufactured by N.E. Chemcat Co., Ltd.) 0.105 g (0.0248 mmol as Pd atomic weight) was added, and the temperature was raised to 105 ° C. in a nitrogen gas atmosphere. After warming and reacting for 4 hours, 27.3 g (0.273 mol) of allyl acetate was added, and heating was continued for 12 hours. After adding pure water (200 g) until the precipitated salt was dissolved, 200 g of toluene was added and maintained at a temperature of about 80 ° C. to confirm that no white precipitate had precipitated. Thereafter, Pd / C was recovered by filtration (a membrane filter having a pore size of 1 micron (pressurization (0.3 MPa) using KST-142-JA manufactured by Advantech)). The organic layer was washed twice with 200 g of water at about 50 ° C. to confirm that the aqueous layer was neutral, separated and concentrated under reduced pressure to give a brown color. As a result of ¹ H-NMR measurement of the brown oily substance, a phenol novolak allyl ether represented by the formula (11) (hereinafter abbreviated as BRG-556-AL) was obtained. The measurement data belonging to the compound represented by formula (11) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.6-4.0 (4H, m, PhCH ₂ Ph), δ 4.4-4.8 (2H, m, C H ₂ CH═CH ₂ ), Δ 5.1-5.3 (1H, m, CH ₂ CH═CH H ), δ 5.3-5.5 (1H, m, CH ₂ CH═C H H), δ 5.8-6.2. _{(1H, m, CH 2 C} H = CH 2), δ6.6-7.3 (12H, m, aromatic).

A magnetic stirring bar and 500 g of the phenol novolak allyl ether obtained in the above synthesis were placed in a 1000 mL eggplant flask and heated at 190 ° C. in a nitrogen gas atmosphere. After 3 hours, it was cooled to give a black solid (550 g, quantitative). As a result of ¹ H-NMR measurement of this black solid, it was confirmed that it contained a phenol novolak allyl substitute represented by formula (12) (hereinafter abbreviated as BRG-556-CL) as a main component. Measurement data belonging to the compound represented by the formula (12) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2H, m, C H ₂ CH═CH ₂ ), δ 3.6-4.0 (5H, m, PhCH ₂ Ph _{, OH), δ4.6-5.0 (1H,} m, CH 2 CH = CH H), δ5.0-5.3 (1H, m, CH 2 CH = C H H), δ5.8-6 _{.1 (1H, m, CH 2} C H = CH 2), δ6.6-7.2 (12H, m, aromatic).

Synthesis Example except that 4,4 ′-(dimethylmethylene) bis [2- (2-propenyl) phenol] in Synthesis Example 1 was changed to the phenol novolak allyl substitute (BRG-556-CL) obtained in the above synthesis. The phenol novolac type allyl ether having an allyl group at the ortho-position or para-position was synthesized using allyl acetate in the same manner as in 1 to obtain a brown oil (yield 92%). As a result of ¹ H-NMR measurement of the brown oily substance, a phenol novolak type allyl ether (hereinafter abbreviated as BRG-556-AL2) having an allyl group at the ortho or para position represented by the formula (13) is a main component. Confirmed as including. Measurement data belonging to the compound represented by the formula (13) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.4-4.0 (4H, m, PhOC H ₂ CH═CH ₂ , PhC H ₂ CH═CH ₂ ), δ 4.3-4.9. (4H, m, PhCH ₂ Ph), δ 5.2-5.3 (4H, m, PhOCH ₂ CHC = H H, PhCH ₂ CH = C H H), δ 5.3-5.5 (2H, m, _{PhOCH 2 CHC = H H, PhCH} 2 CH = CH H), δ5.8-6.2 (1H, m, PhOCH 2 C H C = H 2, PhCH 2 C H = CH 2), δ6.5-7 .3 (12H, m, aromatic).

Synthesis Example 4: Synthesis of a phenol novolac-type glycidyl ether compound (abbreviated as BRG-556-EP2) having a glycidyl group at the ortho-position or para-position. In a 200 mL three-neck round bottom flask, the ortho-position or para-form obtained in Synthesis Example 3 above was added. 20 g (about 106 mmol) of phenol novolac type allyl ether (BRG-556-AL2) having an allyl group at the position, 3.48 g (10.6 mmol) of sodium tungstate monohydrate, 0.52 g (5.27 mmol) of phosphoric acid , 0.51 g (5.27 mmol) of sulfuric acid, and 4.94 g (10.6 mmol) of MTOAHS were added and dissolved in 20 g of toluene. After heating up to 70 degreeC, 61.7 g (0.63 mol) of 35 mass% hydrogen peroxide aqueous solution was dripped over 1 hour, stirring, and also it stirred at 70 degreeC for 2 hours (stirring speed 400rpm). At the beginning of the reaction, the pH of the reaction solution was 1.4, and the pH of the reaction solution after 2 hours of reaction was 3.4. After completion of the reaction, the reaction solution was cooled to room temperature, and then 20 g of water was added to carry out a liquid separation treatment. The organic layer was separated, and 20 g of an aqueous sodium sulfite solution (10% by mass) was added and washed to reduce the remaining hydrogen peroxide. The aqueous layer was removed, and 20 g of water was added and washed again. The organic layer was isolated and the organic solvent (toluene) was distilled off. 15.3 g (81.4 mmol, yield 76.5%) of a brown high-viscosity oil having an epoxy equivalent of 141 and an epoxy equivalent ratio (E / Er = measured epoxy equivalent / theoretical epoxy equivalent) of 1.29 was obtained. It was. As a result of ¹ H-NMR measurement of this brown highly viscous oily substance, it was confirmed that it contained a phenol novolac polyvalent glycidyl compound represented by the formula (14) as a main component. The phenol novolac type polyvalent glycidyl compound represented by the formula (14) is a mixture of 2 to 7 repeating units o, but the epoxy equivalent is almost constant regardless of the repeating units o, so that o = 5 The compound at that time was used as a model skeleton, and the theoretical epoxy equivalent 109 at that time was used as Er. The measurement data belonging to the compound represented by formula (14) is as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 2.5-2.8 (2H, m, PhOC H ₂ CHCH ₂ O), δ 2.8-3.0 (4H, m, PhC H ₂ CHCH ₂ O, PhCH ₂ CHC H ₂ O), δ 3.1-3.4 (2H, m, PhOCH ₂ CHC H ₂ O), δ 3.6-4.0 (6H, m, PhCH ₂ Ph, PhOCH ₂ C) _{H CH 2 O, PhCH 2 C} H CH 2 O), δ6.6-7.2 (12H, m, aromatic).

Synthesis Example 5: Synthesis of substrate (triphenylmethane novolak (polycondensation product of phenol and benzaldehyde) allyl ether (abbreviated as TRI-220-AL2) having an allyl group at ortho- or para-position) Shonol (registered trademark) as a raw material Except for using 500.0 g of triphenylmethane novolak (Shonol (registered trademark) TRI-220, p = 2-7) (manufactured by Showa Denko KK) represented by formula (15) instead of BRG-556 The substrate was synthesized in three steps in the same manner as BRG-556-AL2 in Synthesis Example 3. First, in the first step, a triphenylmethane novolak allyl ether (hereinafter abbreviated as TRI-220-AL) was synthesized and browned. oil was obtained (yield: 94%). the brown oil was the ¹ H-NMR measurement result, triphenyl represented by the formula (16) Measurement data attributable to the compound represented by was confirmed to contain the Tan novolak allyl ether bodies as a main component. Equation (16) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2H, m, PhCHPh), δ 4.5-4.6 (2H, m, C H ₂ CH═CH ₂ ), δ5.2-5.3 (1H, m, CH ₂ CH═CH H ), δ 5.3-5.5 (1H, m, CH ₂ CH═C H H), δ 6.0-6.1 (1H _{, m, CH 2 C H =} CH 2), δ6.6-7.3 (17H, m, aromatic).

Similar to the synthesis of BRG-556-AL2, the triphenylmethane novolak allyl substitute (hereinafter abbreviated as TRI-220-CL) was synthesized in the second step to obtain a brown oil (yield 98%). . As a result of ¹ H-NMR measurement of the brown oily substance, it was confirmed that the compound represented by the formula (17) was contained as a main component. Measurement data belonging to the compound represented by the formula (17) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2H, m, PhCHPh), δ 4.8-4.9 (1H, m, CH H CH═CH ₂ ), δ5 0.0-5.2 (3H, m, C H HCH═CH ₂ , CH ₂ CH═CH H , CH ₂ CH═C H H), δ5.8-6.1 (1H, m, CH ₂ C H _{= CH 2), δ6.6-7.4 (17H} , m, aromatic).

Similar to BRG-556-AL2, the triphenylmethane novolak type allyl ether (hereinafter abbreviated as TRI-220-AL2) was synthesized in the third step to obtain a brown oil (yield 98%). As a result of ¹ H-NMR measurement of the brown oily substance, it was confirmed that the compound represented by the formula (18) was contained as a main component. The measurement data belonging to the compound represented by the formula (18) is as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 2.6-2.9 (2H, m, PhOC H ₂ CH═CH ₂ ), δ 3.1-3.3 (2H, m, PhCHPh), δ4.5-4.9 (2H, m, PhCH H CH═CH ₂ , PhOCH H CH═CH ₂ ), δ 5.0-5.4 (3H, m, PhC H HCH═CH ₂ , PhOC H HCH = _{CH 2, PhCH 2 CH = C} H 2, PhOCH 2 CH = C H 2), δ5.8-6.1 (2H, m, PhCH 2 C H = CH 2, PhOCH 2 C H = CH 2), δ6 6-7.3 (17H, m, aromatic).

Synthesis Example 6: Synthesis of triphenylmethane novolak (polycondensation product of phenol and benzaldehyde) glycidyl ether (abbreviated as TRI-220-EP2) having a glycidyl group at the ortho-position or para-position. 15 g (about 48 mmol) of triphenylmethane novolak-type allyl ether (TRI-220-AL2) having an allyl group at the ortho- or para-position obtained in 5 and 3.48 g (10.6 mmol) of sodium tungstate monohydrate , 0.52 g (5.27 mmol) of phosphoric acid, 0.51 g (5.27 mmol) of sulfuric acid and 4.94 g (10.6 mmol) of MTOAHS were added and dissolved in 20 g of toluene. After heating up to 70 degreeC, 61.7 g (0.63 mol) of 35 mass% hydrogen peroxide aqueous solution was dripped over 1 hour, stirring, and also it stirred at 70 degreeC for 2 hours (stirring speed 400rpm). At the beginning of the reaction, the pH of the reaction solution was 1.4, and the pH of the reaction solution after 2 hours of reaction was 3.4. After completion of the reaction, the reaction solution was cooled to room temperature, and then 20 g of water was added to carry out a liquid separation treatment. The organic layer was separated, and 20 g of an aqueous sodium sulfite solution (10% by mass) was added and washed to reduce the remaining hydrogen peroxide. The aqueous layer was removed, and 20 g of water was added and washed again. The organic layer was isolated, the organic solvent (toluene) was distilled off, and a brown highly viscous oily product having an epoxy equivalent of 184 and an epoxy equivalent ratio (E / Er = epoxy equivalent by actual measurement / theoretical epoxy equivalent) of 1.29 11.4 g (36 mmol, yield 75.7%) was obtained. As a result of ¹ H-NMR measurement of this brown highly viscous oily substance, it was confirmed that it contained a triphenylmethane novolak type polyvalent glycidyl compound represented by the formula (19) as a main component. The triphenylmethane novolak type multivalent glycidyl compound represented by the formula (19) is a mixture of repeating units p of 2 to 7, but the epoxy equivalent is almost constant without depending on the repeating unit p. The compound at the time of 5 was used as a model skeleton, and the theoretical epoxy equivalent 143 at that time was used as Er. Measurement data belonging to the compound represented by the formula (19) is as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 2.4-2.6 (2H, m, PhOC H ₂ CHCH ₂ O), δ 2.6-2.8 (4H, m, PhC H ₂ CHCH ₂ O, PhCH ₂ CHC H ₂ O), δ 2.8-3.0 (2H, m, PhOCH ₂ CHC H ₂ O), δ 3.0-3.3 (2H, m, PhCHPh), δ 3.8- _{4.0 (2H, m, PhOCH 2} C H CH 2 O), δ4.1-4.3 (2H, m, PhCH 2 C H CH 2 O), δ6.6-7.3 (12H, m, aromatic).

The material of the curable resin composition used for the evaluation of the properties of the cured product is described below.
Epoxy resin 1 (corresponding to the polyvalent glycidyl compound (A) of the present invention)
BATG shown in Synthesis Example 2
Epoxy equivalent 119, total chlorine content 33ppm, viscosity 18.5mPa · s (150 ° C)
Epoxy resin 2 (corresponding to the polyvalent glycidyl compound (A) of the present invention)
BRG-556-EP2 shown in Synthesis Example 4
Epoxy equivalent 141, total chlorine content 48ppm, viscosity 168mPa · s (150 ° C)
Epoxy resin 3 (corresponding to the polyvalent glycidyl compound of the present invention)
TRI-220-EP2 shown in Synthesis Example 6
Epoxy equivalent 184, total chlorine content 42ppm, viscosity 242mPa · s (150 ° C)
・ Epoxy resin 4
Commercially available bisphenol A type glycidyl compound JER828EL (Mitsubishi Chemical Corporation)
Epoxy equivalent 191, total chlorine content 302ppm, viscosity 12mPa · s
・ Epoxy resin 5
Commercially available phenol novolac glycidyl compound N740 (manufactured by DIC Corporation)
Epoxy equivalent 179, total chlorine content 1329ppm, viscosity 54mPa · s (150 ° C)
・ Phenolic curing agent 1 (corresponding to the phenolic curing agent (B) of the present invention)
Straight novolac BRG-556 (Showa Denko)
Hydroxyl equivalent weight 103
・ Phenolic curing agent 2 (corresponding to the phenolic curing agent (B) of the present invention)
Phenol / salicylaldehyde polymerization type triphenylmethane novolak hydroxyl equivalent 111
Synthesis and phenolic curing agent 3 (corresponding to the phenolic curing agent (B) of the present invention) in accordance with generally known methods (for example, described in JP2012-193217A)
Naphthol Novolac SN395 (manufactured by Nippon Steel & Sumitomo Metal Corporation)
Hydroxyl equivalent weight 110
・ Phenolic curing agent 4
Cresol novolak CRG-951 (manufactured by Showa Denko KK)
Hydroxyl equivalent weight 118
・ Phenolic curing agent 5
Cresol / salicylaldehyde polymerization type triphenylmethane novolak TRI-002 (manufactured by Showa Denko KK)
Hydroxyl equivalent weight 107
Curing accelerator 1 (corresponding to the curing accelerator (C) of the present invention)
Commercially available triphenylphosphine (made by Hokuko Chemical Co., Ltd.)
Curing accelerator 2 (corresponding to the curing accelerator (C) of the present invention)
Commercially available imidazole catalyst 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.)

  The epoxy equivalent of the epoxy resin, the total chlorine content, the viscosity, and the glass transition temperature of the cured product of the curable resin composition were determined by the following methods.

<Epoxy equivalent>
The epoxy equivalent is determined according to JIS K 7236: 2001. A sample is weighed 0.1 to 0.2 g and placed in an Erlenmeyer flask, and then 10 mL of chloroform is added and dissolved. Next, 20 mL of acetic acid is added, followed by 10 mL of tetraethylammonium bromide solution (100 g of tetraethylammonium bromide dissolved in 400 mL of acetic acid). 4 to 6 drops of crystal violet indicator are added to the obtained solution, titrated with a 0.1 mol / L perchloric acid acetic acid solution, and an epoxy equivalent is determined according to the following formula based on the titration result.
Epoxy equivalent (g / eq) = (1000 × m) / {(V ₁ −V ₀ ) × c}
m: Weight of sample (g)
V ₀ : Amount of perchloric acid acetic acid solution consumed for titration to the end point in the blank test (mL)
V ₁ : Amount of perchloric acid acetic acid solution consumed for titration to the end point (mL)
c: Concentration of perchloric acid acetic acid solution (0.1 mol / L)

<Total chlorine content>
The total chlorine content is determined by burning and decomposing the epoxy resin at a high temperature of 800 ° C. or higher, absorbing the decomposed gas in ultrapure water, and quantifying it by ion chromatography. The ion chromatography is composed of a Dionex IC-1000 and an IonPac AS12A (4 mm) column, and the eluent is measured as a 0.3 mM NaHCO ₃ /2.7 mM Na ₂ CO ₃ aqueous solution at a flow rate of 1.5 mL / min. .

<Viscosity>
The viscosity of the epoxy resin is determined by using a rheometer (manufactured by Anton Paar, MSR301) and using a cone plate (manufactured by Anton Paar, CP25-2, Part. No. 79039) under the following conditions.
Temperature: 150 ° C
Rotation speed: 0.1rpm ~ 1000rpm
Sample weight: about 0.2g

<Glass transition temperature (Tg)>
Measured by thermomechanical measurement (TMA). Using a TMA / SS6100 thermomechanical analyzer manufactured by SII NanoTechnology Co., Ltd., a 5 × 5 × 5 mm test piece under the conditions of a temperature range of −10 to 250 ° C., a heating rate of 5 ° C./min, and a load of 20.0 mN. Use to measure. The temperature at the intersection of two extrapolated lines drawn in the linear region before and after the inflection point based on the transition in the obtained expansion curve is defined as the glass transition temperature.

  Each component shown in Table 1 was blended in the ratio shown in the same table. “OH group / glycidyl group” in the table is the molar ratio of the hydroxyl group of the phenolic curing agent to the total of the glycidyl group and glycidyl ether group of the epoxy resin (number of moles of hydroxyl group of the phenolic curing agent / [glycidyl group of epoxy resin and The total number of moles of glycidyl ether groups]). Each component was dissolved in an organic solvent (using the same weight of acetone as the resin component) and mixed until uniform, and then the solvent was distilled off using an evaporator and a vacuum pump to obtain a mixture.

  The mixture obtained according to the above was powdered using an agate mortar. Grinding was performed until the particle size of the powder became 1 mm or less.

  The obtained powder was formed into a plate-like cured product having a thickness of 5 mm using a heating press machine of Toyo Seiki Seisakusho. The mold used was a Teflon (registered trademark) plate with a central portion cut into a square. It was press-molded at 150 ° C., heat-treated at 150 ° C. for 1 hour, and then post-cured at 200 ° C. for 2 hours using an oven.

  About the obtained hardened | cured material, the glass transition temperature (Tg) was measured. The obtained physical property values are shown in Table 1. When a polyvalent glycidyl compound is used, it is suggested that Tg is higher than that of a general glycidyl compound and that it has good heat resistance.

  When a cured product was prepared using the same phenolic curing agent, a general glycidyl compound having no glycidyl group at the ortho position of the glycidyl ether group was used when the polyvalent glycidyl compound applied in the present invention was used. It shows that it has high heat resistance (glass transition temperature Tg) compared with the case. For example, in Example 1 using a polyvalent glycidyl ether compound (epoxy resin 1) having bisphenol A as a basic skeleton, Tg is higher than that in Comparative Example 2 using a normal bisphenol A glycidyl ether compound (epoxy resin 4). 87 ° C improvement. Similarly, Example 2 using a polyvalent glycidyl ether (epoxy resin 2) having a straight novolak as a basic skeleton is 60 ° C. as compared with Comparative Example 5 using a general straight novolac glycidyl ether compound (epoxy resin 5). A high Tg was obtained.

  The relationship between the type of phenolic curing agent and the Tg of the obtained cured product is the case where a polyvalent glycidyl compound (epoxy resins 1 to 3) applied to the curable resin composition of the present invention is used, and a general glycidyl compound. The tendency is different from the case of using (epoxy resins 4, 5). When a general glycidyl compound (epoxy resins 4 and 5) is used, the heat resistance (Tg) tends to be higher when the curing agent (B) has a more rigid skeleton. The case where the epoxy resin 4 is used appears in the results of Comparative Examples 2 and 3, and the case where the epoxy resin 5 is used appears in the results of Comparative Examples 5 and 6. On the other hand, when the polyvalent glycidyl compound applied to the curable resin composition of the present invention is used, it has a methyl group as compared with a cresol novolak having a methyl group in the ortho position with respect to the hydroxyl group of the phenolic curing agent. The heat resistance (Tg) of the cured product is higher when a straight novolac is used. When Example 1 and Comparative Example 1 are used for the epoxy resin 1, it can be seen that Tg is 26 ° C. higher when a phenolic curing agent having a small steric hindrance is used. Similarly, when Example 2 and Comparative Example 4 are seen for the epoxy resin 2, it can be seen that Tg is 18 ° C. higher when a phenolic curing agent having a small steric hindrance is used. Similarly, a phenol / salicylaldehyde polymerization type triphenylmethane novolak having no methyl group is used in comparison with the case of using a cresol / salicylaldehyde polymerization type triphenylmethane novolak having a methyl group at the ortho position of the reactive functional group (hydroxy group). The higher heat resistance (Tg) is shown when using is used as a curing agent (comparison between Example 4 and Comparative Example 7). From these results, since the functional group density of the polyvalent glycidyl compound is high, it is considered that the reactivity decreases as the steric hindrance around the reactive group of the phenolic curing agent increases.

  Similarly, Examples 5 to 7 show that cured products having good heat resistance can be obtained by using various types of polyvalent glycidyl compounds applied to the present invention and phenolic curing agents in combination.

  The effect of the steric hindrance was examined from the quantitative evaluation of the epoxy curing reaction. Specifically, quantification was attempted using the Kamal model formula (1) based on the Arrhenius formula. This model formula is described, for example, in Journal of Polymer Science, Part B Polymer Physics 2004, 42, 20, 3701-3712, SENI GAKAI Vol 68. No. 4, 2012 and the like, it is widely used in describing the curing reaction of epoxy compounds. In this model formula, the reaction rate is calculated using the relationship of the following formulas (1) to (3).

式中、α：硬化率、ｍ、ｎ：反応次数、Ｅ_１、Ｅ_２：活性化エネルギー、Ａ_１、Ａ_２：頻度因子、Ｒ：気体定数、Ｔ：絶対温度、Ｋ_１、Ｋ_２：反応速度定数）である。硬化率αは示差走査型熱量測定（ＤＳＣ測定）より求めることが可能である。具体的には１００℃から２５０℃までの昇温速度を５、１０、２０、４０℃／ｍｉｎとして反応熱を測定し、任意の温度Ｔまでの積分値を全ピークの積分値で割ることで計算できる。αに対してｄα／ｄＴをプロットすると山型の曲線が得られる。山形となるのは、温度が上がるにつれて反応速度が上昇するがある程度まで架橋が進行すると反応の支配が拡散律速に移行し反応速度が落ちるためである。得られたグラフについて表計算ソフト（例えばマイクロソフト社のＥＸＣＥＬ（登録商標）ソフトのソルバー機能）を用いてフィッティングを行うと上記数式１の各定数が概算できる。

In the formula, α: curing rate, m, n: reaction order, E ₁ , E ₂ : activation energy, A ₁ , A ₂ : frequency factor, R: gas constant, T: absolute temperature, K ₁ , K ₂ : Reaction rate constant). The curing rate α can be obtained by differential scanning calorimetry (DSC measurement). Specifically, the heat of reaction is measured at a rate of temperature increase from 100 ° C. to 250 ° C. at 5, 10, 20, 40 ° C./min, and the integrated value up to an arbitrary temperature T is divided by the integrated value of all peaks. Can be calculated. When dα / dT is plotted against α, a mountain-shaped curve is obtained. The reason why the shape is Yamagata is that the reaction rate increases as the temperature rises, but when the crosslinking proceeds to a certain extent, the control of the reaction shifts to diffusion-controlled and the reaction rate decreases. When the obtained graph is fitted using spreadsheet software (for example, the solver function of EXCEL (registered trademark) software manufactured by Microsoft Corporation), the constants of Equation 1 can be estimated.

  The exothermic behavior of the curable resin composition of Example 1 was measured using DSC, and a mountain-shaped curve obtained by applying to the above model is shown as an actual measurement value in FIG. In addition, a mountain-shaped curve obtained as a result of fitting with actual measurement values using spreadsheet software is shown as a calculation value in FIG. Table 2 shows each constant of the mathematical formula (1) obtained from the fitting result.

<Differential scanning calorimetry (DSC measurement)>
Using a Neztch DSC / differential scanning calorimeter, the temperature range is 30 ° C to 250 ° C, the heating rate is 5 ° C / min, 10 ° C / min, 20 ° C / min, 40 ° C / min. A 10 mg sample is weighed and measured under a nitrogen gas stream. The integral of the obtained exothermic curve was calculated and used for analysis as described above.

By substituting the calculation results of the respective coefficients obtained by fitting into the Arrhenius equations (2) and (3), reaction rate constants K ₁ and K ₂ are obtained. Effect of resins are known to be reflected in terms of K ₂ on the reaction rate. The value of K ₂ becomes 0.042 (temperature calculation at 150 ℃ (423K)).

The above experiments and also performed for Comparative Example 4 to analyze the reaction rate constant K ₂ and the result of computation 0.007, and this value suggests that low reactivity of Comparative Example 4 than in Example 1.

  These results indicate that the methyl group is located at the ortho position of the reactive hydroxyl group as compared with the case of using cresol novolak (CRG-951) having a methyl group at the ortho position of the reactive hydroxyl group of the phenolic curing agent as described above. The direction using BRG-556 which does not have has high reactivity, and supports the tendency for the heat resistance of hardened | cured material to become high.

  By using a curable resin composition in which the polyvalent glycidyl compound of the present invention and a specific phenolic curing agent are used in combination, the crosslinking density in the resin can be increased, and the heat resistance, rigidity, adhesiveness, etc. are excellent. A cured product can be obtained. Therefore, the curable resin composition of the present invention can be suitably used for semiconductor encapsulants, particularly power semiconductor encapsulants that require high heat resistance.

Claims (10)

  Curing comprising a polyvalent glycidyl compound (A) having a glycidyl group and a glycidyl ether group bonded to the same aromatic ring in the molecule, and a phenolic curing agent (B) having no substituent at the ortho position of the phenolic hydroxyl group Resin composition. The polyvalent glycidyl compound (A) is a compound represented by the general formula (1), and the epoxy equivalent of the compound is E, and all R ¹ and R ² having the skeleton of the compound are represented by the formula (3). The curable resin composition according to claim 1, wherein E / Er is 1.01-1.60, where Er is the theoretical epoxy equivalent of the compound represented by formula (1).

(Wherein, R ¹ and R ² are each independently a group represented by the following formula (2) or (3), and Q are each independently represented by the formula: —CR ³ R ⁴ —. An alkylene group, a cycloalkylene group having 3 to 12 carbon atoms, an arylene group composed of a single aromatic ring having 6 to 10 carbon atoms, or an arylene group formed by bonding an aromatic ring having 2 to 3 carbon atoms and 6 to 10 carbon atoms, A divalent alicyclic condensed ring having 7 to 12 carbon atoms, or a divalent group obtained by combining these, R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carbon An alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 to 50.)

(In formula (2), R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an alkyl group having 6 to 10 carbon atoms. Represents an aryl group, and R ⁸ , R ⁹ and R ¹⁰ in formula (3) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a carbon number. Represents 6 to 10 aryl groups.) The polyvalent glycidyl compound (A) is bisphenol-A, bisphenol-F, phenol novolak, triphenylmethanephenol, biphenyl aralkyl type phenol, phenyl aralkyl type phenol, or phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton or both ends. _3. A glycidyl compound having a basic skeleton of any one of phenols having an unsubstituted tetrahydrodicyclopentadiene skeleton to which —CH ₂ — is bonded, wherein R ² is located at an ortho position or a para position with respect to OR ¹ . The curable resin composition described in 1.   The phenolic curing agent (B) is any of phenol novolak resin, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene / phenol polymerization type resin, benzaldehyde / phenol polymerization type novolak resin, or terpene / phenol polymerization type resin. The curable resin composition as described in any one of Claims 1-3.   The curable resin composition according to claim 4, wherein the phenolic curing agent (B) is a phenol novolac resin.   The molar ratio of hydroxyl groups in the phenolic curing agent (B) to the total of glycidyl groups and glycidyl ether groups in the polyvalent glycidyl compound (A) (number of moles of hydroxyl groups in the phenolic curing agent (B) / [polyvalent glycidyl compound) The total number of moles of glycidyl group and glycidyl ether group in (A)] is 0.8 to 1.0, and the curable resin composition according to any one of claims 1 to 5.   The curable resin composition according to any one of claims 1 to 6, further comprising a curing accelerator (C).   The curable resin composition according to any one of claims 1 to 7, further comprising a filler (D).   9. The filler according to claim 8, wherein the filler (D) is an inorganic filler selected from the group consisting of amorphous silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, and mixtures thereof. Curable resin composition.   The curable resin composition according to claim 9, which is for semiconductor encapsulation.

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