JP6692471B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition. More specifically, the present invention relates to a curable resin composition containing a polyvalent glycidyl compound (hereinafter sometimes referred to as an epoxy compound or an epoxy resin) which is excellent in heat resistance and electrical properties and which 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 coatings, civil engineering, and electrical fields. 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., have water resistance, adhesiveness, mechanical properties, heat resistance, It has excellent electrical insulation and economy, and is widely used in combination with various curing agents.

  The glycidyl compound is designed to meet the desired 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 also includes studies on combinations with curing agents and the like. For example, in a phenol novolac type epoxy resin, by adjusting the degree of polymerization of the glycidyl compound, the molecular weight distribution, etc., the fluidity during thermosetting can be changed, and the heat resistance and adhesiveness of the cured product can be controlled. be able to.

  As one aspect relating to molecular design, a polyvalent glycidyl compound having three or more glycidyl groups in one molecule is a cured product using the same as a glycidyl compound having two or less glycidyl groups in one molecule. It is known that heat resistance is improved. This is because the amount of reactive functional groups contained per molecule is increased, 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 is increased, This is because the micro movement of is controlled. It is also known that when the density of glycidyl groups in the composition is increased, the number of polar sites such as hydroxyl groups in the cured product is increased, so that the adhesion between the adherend such as metal and inorganic material and the cured product is improved. Has been.

  As a method of obtaining a glycidyl compound having a high functional group density in the molecule, for example, a method of introducing two or more glycidyl groups into the aromatic ring skeleton of a compound having an aromatic ring can be mentioned. 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 the para position with respect to the glycidyl ether group bonded to the phenol moiety, and the like. Be done. The glycidyl ether group is a combination of a glycidyl group and an oxygen atom, and thus includes a glycidyl group.

  Examples of the polyvalent glycidyl compound having a glycidyl group at the ortho position or the para position with respect to the glycidyl ether group bonded to the phenol moiety include, for example, a compound having bisphenol F as a basic skeleton in Patent Document 1 (JP-A-63-142019). Is disclosed.

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

JP-A-63-142019

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

  The present 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 phenol-based curing agent. It has been found that a cured product having good quality can be 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, and a phenolic curing agent (B) having no substituent at the ortho position of the phenolic hydroxyl group. A curable resin composition containing:
[2] The polyvalent glycidyl compound (A) is a compound represented by the general formula (1), the epoxy equivalent of the compound is E, and all R ¹ and R ² have the skeleton of the compound and are represented by the formula The curable resin composition according to [1], wherein E / Er is 1.01 to 1.60, where Er is the theoretical epoxy equivalent of the compound that is the group represented by (3).

(In the formula, R ¹ and R ² are each independently a group represented by the following formula (2) or (3), and Q is each independently a formula: —CR ³ R ⁴ — An alkylene group represented, 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 an arylene group formed by bonding an aromatic ring having 2 to 3 carbon atoms of 6 to 10; It is a divalent alicyclic condensed ring having 7 to 12 carbon atoms, or a divalent group combining these, and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom. It is 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.)

(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 alkyl group having 6 to 10 carbon atoms. It 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. It represents an aryl group of 6 to 10.)
[3] The polyvalent glycidyl compound (A) is bisphenol-A, bisphenol-F, phenol novolac, triphenylmethane phenol, biphenylaralkyl type phenol, phenylaralkyl type phenol, or an unsubstituted tetrahydrodicyclopentadiene skeleton phenol. Alternatively, it is a glycidyl compound having either basic skeleton of an unsubstituted tetrahydrodicyclopentadiene skeleton in which —CH ₂ — is bonded to both ends, and R ² is located in the ortho or para position with respect to OR ¹ . The curable resin composition according to [2].
[4] The phenolic curing agent (B) is any one of a phenol novolac resin, a phenol aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene / phenol polymerization resin, a benzaldehyde / phenol polymerization novolac resin, or a 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) (the number of moles of hydroxyl groups in the phenolic curing agent (B) / [ The total number of glycidyl groups and glycidyl ether groups of the valent glycidyl compound (A)] is 0.8 to 1.0, and the curable resin composition according to any one of [1] to [5].
[7] The curable resin composition according to any one of [1] to [6], which further contains a curing accelerator (C).
[8] The curable resin composition according to any one of [1] to [7], which further contains 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 a mixture thereof. [8] The curable resin composition according to.
[10] The curable resin composition according to [9], which is used for semiconductor encapsulation.

  By using the curable resin composition in which the polyhydric glycidyl compound of the present invention and a specific phenolic curing agent are used in combination, the crosslink density in the resin can be increased, and heat resistance, rigidity, and adhesiveness are excellent. A cured product can be obtained. Therefore, the curable resin composition of the present invention can be suitably used as a semiconductor encapsulant, particularly as a power semiconductor encapsulant requiring high heat resistance.

2 is a ¹ H-NMR spectrum of the product obtained in Synthesis Example 2. 3 is a ¹ H-NMR spectrum of the product obtained in Synthesis Example 4. 3 is a ¹ H-NMR spectrum of the product obtained in Synthesis Example 6. It is a figure which shows the fitting of the curing reaction rate calculated | required by measuring the exothermic behavior of the curable resin composition of Example 1 using DSC, and Kamal model formula (1).

  Hereinafter, the present invention will be described in detail. The curable resin composition of the present invention comprises 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. It is characterized by containing a system hardening 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。 [Polyvalent 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. Specific examples thereof include compounds represented by the general formula (1).

In the formula, R ¹ and R ² are each independently a group represented by the following formula (2) or (3), and Q is each independently represented by the formula: —CR ³ R ⁴ —. Alkylene group, 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 an arylene group formed by bonding an aromatic ring having 2 to 3 carbon atoms of 6 to 10 (for example, An arylene group having a biphenyl skeleton as an arylene group having two aromatic rings bonded thereto, an arylene group having a triphenyl skeleton as an arylene group having three aromatic rings bonded thereto, and a carbon number of 7 to 12 Is a divalent alicyclic fused ring or a divalent group in which these are combined, and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a C 2 to 10 carbon atom. Alkenyl group having 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 group having 6 to 10 carbon atoms. represents a group, ^R 8, ^{R 9} and ^{R 10} in the formula (3) are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a carbon of 3 to 12 carbon atoms 6 10 represents an aryl group. * In the formulas (2) and (3) means a bond with the oxygen atom or the carbon atom constituting the aromatic ring.

The curable resin composition contains a compound represented by the general formula (1), the epoxy equivalent of the compound is E, and all the 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 the group is Er, E / Er is preferably 1.01 to 1.60. In the present specification, the “epoxy equivalent” means a value obtained by dividing the molecular weight of the glycidyl compound by the number of oxirane rings in the molecule, and is determined by the epoxy equivalent measuring method described later. When the epoxy equivalent ratio (E / Er) is larger 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 deteriorated. 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. Since it takes time to purify to make the epoxy equivalent ratio (E / Er) smaller than 1.01, the epoxy equivalent ratio (E / Er) is more preferably 1.02 or more in consideration of productivity. It is preferably 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 both allyl groups (R ^{5 to} R in the formula (2)). ⁷ are all hydrogen atoms), 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 Equivalent 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 If the compound is, E / Er is 1. When the method for producing a polyvalent glycidyl compound described below is used, a plurality of kinds represented by the general formula (1) having the same basic skeleton in the reaction product (the formula (2) or the formula (as R ¹ and R ² The compounds of (3) having different numbers of groups are usually contained in the product. In that case, the epoxy equivalent E becomes the epoxy equivalent of the entire mixture of plural kinds of compounds.

As the compound represented by the general formula (1), preferred examples of R ¹ and R ² include groups represented by the formula (2) or the formula (3) in which all R ^{5 to} R ¹⁰ are hydrogen atoms. Preferable examples of Q include a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or R ³ and R ⁴ each independently as an alkylene group represented by the formula: —CR ³ R ⁴ —. Those which are naphthyl groups can be mentioned. The cycloalkylene group having 3 to 12 carbon atoms is preferably 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 having 6 to 10 carbon atoms. Preferable examples of the arylene group include a phenylene group and a biphenyldiyl group. The divalent alicyclic condensed ring having 7 to 12 carbon atoms is preferably a divalent tetrahydrodicyclopentadiene ring. Preferred examples of the divalent group formed by combining _{these, -CH 2 -Ph-Ph-CH} 2 - (Ph refers to unsubstituted benzene ring herein) group, and _-CH 2 -Ph-CH ₂ -groups may be mentioned. Preferred specific compounds, bisphenol -A, bisphenol -F, phenol novolac, triphenylmethane phenol, e.g. _{-CH 2 -Ph-Ph-CH 2} - biphenyl aralkyl type phenol having a skeleton, for example, _-CH 2 -Ph A basic skeleton of a phenylaralkyl-type phenol having a —CH ₂ — skeleton, or a phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton or a phenol of an unsubstituted tetrahydrodicyclopentadiene skeleton in which —CH ₂ — is bonded to both ends is used. A glycidyl compound having R ² in the ortho position or the para position with respect to OR ¹ is simpler in production and more preferable.

[Method for producing polyvalent glycidyl compound]
Next, a method for producing the polyvalent glycidyl compound (A) used in the curable resin composition of the present invention will be described. The method for producing the polyvalent glycidyl compound of the present invention is not particularly limited, and a known method can be used. As one preferable method, the carbon-carbon double bond of the 2-alkenyl group and the 2-alkenyl ether group of the compound having the 2-alkenyl group and the 2-alkenyl ether group or the glycidyl ether group bonded to the same aromatic ring is replaced by It can be obtained by oxidation (glycidylation) in the presence of two or more kinds of acids containing tungstic acid, a quaternary ammonium salt, and at least phosphoric acid as a catalyst using an aqueous solution of hydrogen oxide as an oxidizing agent.

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, but 2-alkenyl ether. A compound having a 2-alkenyl group in the ortho position or the para position with respect to the group or the glycidyl ether group is preferable because it is relatively easily available. Examples of suitable 2-alkenyl compounds include compounds represented by the following general formula (4).

In the formula, R ¹¹ is each 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 having a single aromatic ring having 6 to 10 carbon atoms, or 6 to 8 carbon atoms having 2 to 3 carbon atoms. An arylene group having 10 aromatic rings bonded to each other, a divalent alicyclic condensed ring having 7 to 12 carbon atoms, or a divalent group in which these are combined, and 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. Represents a group, and R ¹⁸ , R ¹⁹ and R ²⁰ in formula (6) 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. 10 represents an aryl group. * In the formulas (5) and (6) means a bond to the oxygen atom or the carbon atom constituting the aromatic ring.

Specific examples of the 2-alkenyl compound represented by the general formula (4) include bisphenol-A, bisphenol-F, phenol novolac, triphenylmethane phenol, biphenylaralkyl type phenol, phenylaralkyl type phenol, or unsubstituted. -CH 2 phenol or both ends of tetrahydrodicyclopentadiene skeleton _- has one of the basic skeleton of bound unsubstituted tetrahydrodicyclopentadiene skeleton phenol, R ² with respect to oR ¹ is ortho or para position 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. , A compound having a 2-alkenyl group positioned at the ortho position or para position of the phenolic hydroxyl group is obtained by converting the compound into a corresponding 2-alkenyl ether compound and subsequently undergoing Claisen rearrangement and derivatization into a phenol compound. 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.

  For the conversion step to the 2-alkenyl ether compound after the Claisen rearrangement, for example, a method described in US Pat. No. 5,578,740, which uses an allyl carboxylate as a allylating agent and a metal catalyst, is known. Besides, J. Muzart et al. Organomet. Chem. , 326, pp. C23-C28 (1987) and the like disclose a method of converting to an allyl ether using a metal catalyst. By these methods, a 2-alkenyl ether compound having a 2-alkenyl group as a raw material of a polyvalent glycidyl compound in the ortho position or the para position can be obtained. Examples of the allyl etherification reaction of the 2-alkenylated phenol at the ortho position include allyl acetate, allyl alcohol, allyl carbonate, allyl carbamate, and allyl chloride, which are industrially inexpensive. 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 the phenolic hydroxyl group with epihalohydrin.

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

  In the method for producing a polyvalent glycidyl compound, the carbon-carbon double bonds of the 2-alkenyl group and the 2-alkenyl ether group of the 2-alkenyl compound represented by the formula (4), which is the reaction substrate, are converted into an aqueous hydrogen peroxide solution. Is used as an oxidizing agent to oxidize (glycidylate). 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 for separation, it is preferable that the hydrogen peroxide aqueous solution has a high concentration, but on the other hand, an excessively high concentration and / or an excessive amount of hydrogen peroxide aqueous solution may be used. It is preferable not to use it from the viewpoint of economical efficiency and safety.

  The total amount of the hydrogen peroxide solution used is 1.0 to 5.0 equivalents, preferably 1.1, with respect to the carbon-carbon double bond of the 2-alkenyl group and the 2-alkenyl ether group of the reaction substrate. ~ 3.0 equivalents, more preferably 1.2-2.0 equivalents. If it is less than 1.0 equivalent, theoretically all the carbon-carbon double bonds of the 2-alkenyl group and the 2-alkenyl ether group cannot be oxidized. If the amount is more than 5.0 equivalents, a large amount of reducing agent is needed 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 progresses. It is preferable to maintain the hydrogen peroxide concentration in the reaction solution within the range of about 0.1 to about 30% by mass, and more preferably about 5 to about 10% by mass by supplementing to this decrease. If it is less than 0.1% by mass, the productivity will be poor, while if it is more than 30% by mass, the explosiveness in the mixed composition of the solvent and water may be increased, which may be dangerous.

  The addition of the hydrogen peroxide aqueous solution to the reaction solution is carried out for 0.1 to 2 hours, preferably 0.5 to 1.5 hours from the start of the addition. When the addition time of the hydrogen peroxide aqueous solution becomes long (the addition speed is slow), the hydrogen peroxide concentration in the system decreases, the efficiency of the oxidation reaction decreases, and hydrolysis may occur in competition. Note that if a large amount of aqueous hydrogen peroxide solution is added to the reaction solution at the beginning of the reaction, the reaction may proceed rapidly and may be dangerous. It is preferable to add it by dropping 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 is completed. It is preferable to continue the reaction while stirring the reaction solution, and it is preferable to use a magnetic stirrer or a stirrer having a stirring blade for stirring. The stirring speed is generally in the range of 100 to 2000 rpm, preferably in the range of 300 to 1500 rpm. The reaction liquid is a two-phase system of a 2-alkenyl compound simple substance which is a reaction substrate or an organic phase containing a 2-alkenyl compound dissolved in an organic solvent and an aqueous phase containing hydrogen peroxide, and these two phases are emulsions. It is preferable to stir the mixture so that With the progress of the oxidation (glycidylation) reaction of the carbon-carbon double bond of the 2-alkenyl group and the 2-alkenyl ether group, a glycidyl compound is produced and the viscosity of the reaction solution increases. To prevent hydrolysis of the glycidyl group of the glycidyl compound that is the intermediate product or the final product and the by-product of the gel-like substance caused by it, the reaction is continued within the range of 2 to 6 hours after the addition of the aqueous hydrogen peroxide solution. After that, stirring and heating are stopped to complete the oxidation reaction. If the reaction is stopped in less than 2 hours, a large number of carbon-carbon double bonds of the 2-alkenyl group and the 2-alkenyl ether group of the reaction substrate remain and the yield of the desired product is low. If the reaction is continued for longer than 6 hours, the hydrolyzate becomes a main product and a gelled product is formed in some cases, so that the post-treatment process of the reaction solution becomes complicated and the yield of the target product decreases.

  Oxidation (glycidylation) using an aqueous hydrogen peroxide solution can be carried out in the presence of a catalyst containing a tungsten compound, a quaternary ammonium salt, and two or more kinds of acids containing at least phosphoric acid. Since these compounds are relatively inexpensive, oxidation of the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound using hydrogen peroxide as an oxidant should be performed at low cost. You can

  As the tungsten compound used as a catalyst, a compound that generates a tungstate anion in water is suitable, and for example, tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, phosphotungstic acid, ammonium tungstate, potassium tungstate. Examples thereof include monohydrate and dihydrate, sodium tungstate monohydrate and dihydrate, and tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate monohydrate and dihydrate. The 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 generate tungstate anions in water is higher when about 0.2 to about 0.8 mol of counter cation is present with respect to 1 mol of tungstate anions. As a method for preparing such a tungsten composition, for example, tungstic acid and an alkali metal salt of tungstic acid may be mixed so that the tungstate anion and the counter cation have the above ratio, or tungstic acid is mixed with an alkali compound ( Alkali metal or alkaline earth metal hydroxides, carbonates, etc.) or by combining tungstic acid alkali metal salts or alkaline earth metal salts with acidic compounds such as phosphoric acid, sulfuric acid and other mineral acids. Good. Preferred examples of these include a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and a mineral acid, or a mixture of tungstic acid and an alkali compound.

  The amount of the tungsten compound used as a catalyst is about 0.0001 to about 0.001 to about the carbon-carbon double bond of the 2-alkenyl group and the 2-alkenyl ether group of the 2-alkenyl compound which is the reaction substrate for the tungsten element. 20 mol%, preferably about 0.01 to about 20 mol%.

  As the quaternary ammonium salt used as a catalyst, a quaternary organic ammonium salt in which the total number of carbon atoms of the substituent bonded to the nitrogen atom is 6 or more and 50 or less, preferably 10 or more and 40 or less is oxidized (glycidylation). It is preferable because the activity of the reaction is high.

  The quaternary ammonium salt, trioctyl methyl ammonium chloride, trioctyl ethyl ammonium chloride, dilauryl dimethyl ammonium chloride, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, tricapryl methyl ammonium chloride, dichloro chloride Chlorides such as decyldimethylammonium, tetrabutylammonium chloride, benzyltrimethylammonium chloride and benzyltriethylammonium chloride; trioctylmethylammonium bromide, trioctylethylammonium bromide, dilauryldimethylammonium bromide, lauryltrimethylammonium bromide, Stearyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium bromide, bromide Bromides such as lycaprylmethylammonium, didecyldimethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide; trioctylmethylammonium iodide, trioctylethylammonium iodide, diiodide Lauryl dimethyl ammonium, lauryl trimethyl ammonium iodide, stearyl trimethyl ammonium iodide, lauryl dimethyl benzyl ammonium iodide, tricapryl methyl ammonium iodide, didecyl dimethyl ammonium iodide, tetrabutyl ammonium iodide, benzyl trimethyl ammonium iodide, iodo Iodide such as benzyltriethylammonium trioxide; trioctylmethylammonium hydrogen phosphate, hydrogen phosphate Trioctylethylammonium, dilauryldimethylammonium hydrogenphosphate, lauryltrimethylammonium hydrogenphosphate, stearyltrimethylammonium hydrogenphosphate, lauryldimethylbenzylammonium hydrogenphosphate, tricaprylmethylammonium hydrogenphosphate, phosphoric acid Didecyldimethylammonium hydride, tetrabutylammonium hydrogenphosphate, benzyltrimethylammonium hydrogenphosphate, benzyltriethylammonium hydrogenphosphate, and the like; trioctylmethylammonium hydrogen sulfate, trioctyl hydrogen sulfate sulfate Ethyl ammonium, dilauryl dimethyl ammonium hydrogen sulfate, lauryl trimethyl ammonium hydrogen sulfate, stearyl trimethyl ammonium hydrogen sulfate, water sulfate Hydrogen sulfate such as lauryl dimethyl benzyl ammonium hydride, tricapryl methyl ammonium hydrogen sulfate, didecyl dimethyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen sulfate, benzyl trimethyl ammonium hydrogen sulfate, and benzyl triethyl ammonium hydrogen sulfate can be used. Can be mentioned.

  These quaternary ammonium salts may be used alone or in combination of two or more. The amount thereof used is preferably about 0.0001 to about 10 mol%, more preferably about 0.001 to about 10 carbon% of the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound as the reaction substrate. It is selected from the range of 01 to about 10 mol%.

  When a phase transfer catalyst having a chloride ion, a bromide ion or an 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 removing agent 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, the operation becomes complicated because a step of removing the quaternary ammonium salt is required. Therefore, it is preferable to use phosphonic acid hydride or hydrogen sulfate as the quaternary ammonium salt, and more preferable to use hydrogen sulfate.

  In the method for producing a polyvalent glycidyl compound of the present invention, phosphoric acid is used as a cocatalyst. Phosphoric acid forms an active species by coordinating an oxygen atom with a tungsten metal center that is a catalyst metal. Moreover, the pH of the reaction liquid is controlled to 1.0 to 4.0 by using an acid other than phosphoric acid in combination. The pH of the reaction solution is preferably 1.2 to 3.8, more preferably 1.4 to 3.5. If the pH of the reaction solution is higher than 4.0, the reaction rate will be lowered and the productivity will be lowered. On the other hand, if it is lower than 1.0, the hydrolysis of the glycidyl group will proceed to tend to lower the yield. The amount of phosphoric acid used is preferably about 0.1 to about 10 mol%, more preferably about 10 mol% with respect to the carbon-carbon double bond of the 2-alkenyl group and 2-alkenyl ether group of the 2-alkenyl compound as 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. 0% to the carbon-carbon double bond of the 2-alkenyl group and the 2-alkenyl ether group of the 2-alkenyl compound as the reaction substrate. It is selected from the range of 01 to about 10 mol%. Among these acids, sulfuric acid is preferable because it has a large buffering effect and easily maintains the pH in the range of 1.0 to 4.0.

  In the glycidylation reaction by oxidation, an aqueous solution of hydrogen peroxide and the above-mentioned catalyst are mixed without using an organic solvent or, if necessary, with an organic solvent to promote the glycidylation reaction of the 2-alkenyl compound as a reaction substrate. be able to. When a solvent is used, the reaction rate becomes slow, and depending on the solvent, an undesired reaction such as a hydrolysis reaction may easily proceed. Therefore, it is necessary to select appropriately. When the viscosity of the 2-alkenyl compound represented by the formula (4) as the reaction substrate is too high or when it is a solid, the 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 to use only the minimum necessary amount in terms of production cost, and the amount of the organic solvent used is preferably about 300 parts by mass or less, more preferably 100 parts by mass of the 2-alkenyl compound. It is 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 first charged into the reactor to keep the reaction temperature as constant as possible while the hydrogen peroxide aqueous solution is reacted. It is better to add gradually while checking that it is consumed in. 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, side reactions increase, and if it is too low, the consumption rate of hydrogen peroxide becomes slow and the hydrogen peroxide may accumulate in the reaction solution. Therefore, the reaction temperature is preferably about 40 to about 100 ° C. , More preferably in the range of about 50 ° C to about 80 ° C. Both the addition of the aqueous hydrogen peroxide solution and the reaction after the addition are preferably carried out 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. In that case, a saturated aqueous solution of an inorganic compound is mixed in the aqueous layer to give a difference in specific gravity between the organic layer and the organic extraction solvent. Bilayer separation can be performed without using. In particular, since the specific gravity of the tungsten compound is heavy, in order to bring the water layer to the lower layer, a tungsten compound which exceeds the above-mentioned amount which is originally required as a catalyst may be used. In this case, it is preferable to reuse the tungsten compound from the water layer to enhance the utilization efficiency of the tungsten compound.

  On the contrary, depending on the substrate, the specific gravity of the organic layer may be close to 1.2. In such a case, by adding water to bring the specific gravity of the water layer close to 1, the water content in the upper layer is increased. It is possible to bring an organic layer as a layer or a lower layer. Further, the extraction of the reaction liquid can be carried out by using an organic solvent such as toluene, cyclohexane, hexane or methylene chloride, and an optimum separation method can be selected depending on the situation.

In this way, the organic layer separated from the aqueous layer is concentrated, or after being concentrated as necessary, the polyvalent glycidyl compound obtained is removed by a usual method such as distillation, chromatographic separation, recrystallization, or sublimation. You can The polyvalent glycidyl compound is of 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 in which the compounds are usually contained. This mixture can be separated into each compound using a known separation method, if necessary, but can also be applied to the curable resin composition of the present invention as it is.

[Phenolic curing agent (B)]
The curable resin composition of the present invention is used together with a curing agent for curing the above-mentioned polyvalent glycidyl compound (mixture) (A). 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.

  Since the polyvalent glycidyl compound (A) has a glycidyl group and a glycidyl ether group bonded to the same aromatic ring and the reaction points are close to each other in steric distance, the polyvalent glycidyl compound (A) is used as a phenol-based curing agent for the curable resin composition of the present invention. , 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 phenol-based curing agents include polyphenols such as phenol novolac resin, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene / phenol polymerization resin, benzaldehyde / phenol polymerization novolac resin, and terpene / phenol polymerization resin. Examples thereof include compounds, and among these, phenol novolac resins having particularly low steric hindrance in the vicinity of phenolic hydroxyl groups are preferable. Compared to these phenolic curing agents, when a phenolic curing agent such as a cresol novolac resin having a substituent at the ortho position of the phenolic hydroxyl group at the reaction point, for example, a methyl group is used, the reactivity due to high steric hindrance is increased. Is reduced. As will be described later, this shows an opposite tendency to the case where a general phenol novolac type glycidyl compound having one glycidyl ether group bonded to one aromatic ring as a glycidyl compound is used in combination with a phenolic curing agent. .. Incidentally, in a phenol novolac resin or the like, there is a case where a site bonded to a unit having an adjacent aromatic ring is bonded to an ortho position with respect to a phenol hydroxyl group, but this site is the ortho position of the phenolic hydroxyl group in the present specification. Is not a 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 the methyl group of cresol novolac resin.

  The blending amount of the phenol-based curing agent (B) is the molar ratio of the hydroxyl group of the phenol-based curing agent (B) to the total of the glycidyl group and the glycidyl ether group of the polyvalent glycidyl compound (mixture) (A) (phenol-based curing agent. The number of moles of the hydroxyl group of (B) / [the total number of moles of the glycidyl group and the glycidyl ether group of the polyvalent glycidyl compound (A)] is preferably in the range of 0.8 to 1.0. The above molar ratio is more preferably about 0.85 to about 0.99, further preferably about 0.90 to about 0.98. When the above 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 decreases. On the other hand, when the total of the glycidyl group and the glycidyl ether group of the polyvalent glycidyl compound (A) is stoichiometrically small with respect to the hydroxyl groups of the phenolic curing agent (B), that is, when the above molar ratio exceeds 1.0, The Tg of the cured product tends to be 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; and tertiary tertiary compounds 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; octyl acid Examples thereof include tin compounds such as tin and dibutyltin dilaurate; zinc compounds such as zinc octylate; metal catalysts such as acetylacetonato complexes of aluminum, chromium, cobalt, zirconium and the like. These curing accelerators may be used alone or in combination of two or more kinds.

  The compounding amount of the curing accelerator is not particularly limited, but is usually 0.01 to 5 parts by mass with respect to 100 parts by mass of the curing component of the 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 not to be obtained, and if it exceeds 5 parts by mass, the coloration of the cured product, heat resistance, light resistance and the like are deteriorated. May occur. A more preferable range of the compounding 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, which 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 curing component of the curable resin composition" means that the total amount of the components contributing to the curing in these curable resin compositions 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 the curable resin composition of the present invention is used for semiconductor encapsulation, an inorganic filler that is insulative is added in order to reduce the thermal expansion coefficient of the cured product. This inorganic filler is not particularly limited, and known ones 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 lowering the viscosity, a spherical amorphous silica is particularly preferable. The inorganic filler may be surface-treated with a silane coupling agent or the like, but may not be surface-treated. The average particle size of these inorganic fillers is 0.1 to 20 μm, and the maximum particle size is preferably 75 μm or less, particularly preferably 20 μm or less. When the average particle diameter is within this range, the viscosity of the curable resin composition does not become excessively high, and the composition can be injected appropriately into narrow pitch wiring portions, narrow gap portions, and the like. In the present specification, the "average particle size" is a volume cumulative particle size D ₅₀ measured by a laser diffraction / scattering particle size distribution measuring device, and the "maximum particle size" is a diameter or an ellipse if the particles are spherical. The shape is the long diameter, the needle shape is the long axis dimension, the polygonal shape is the longest side (triangle) or the longest diagonal line (quadrangle or more), and the other dimension is the maximum size. The content of the inorganic filler in the curable resin composition can be appropriately determined according to the application. For example, for semiconductor encapsulation, 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 adhesiveness. The coupling agent is not particularly limited, and examples thereof include 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 alone or in combination of two or more.

  The amount of the coupling agent compounded is usually 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin composition. If it is less than 0.1 part by mass, the compounding effect of the coupling agent may not be sufficiently exerted, and if it exceeds 5 parts by mass, the excess coupling agent is volatilized 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 and includes, for example, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4. '-Butylidene bis (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, nonyldiphenyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene, 9,10-dihydro-9. Phosphorus 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; iron And metal-based antioxidants such as zinc and nickel. These antioxidants may be used alone or in combination of two or more.

  The content of the above antioxidant is usually 0.001 to 2 parts by mass with respect to 100 parts by mass of the curable resin composition. If the amount is less than 0.001 part by mass, the compounding effect of the antioxidant may not be sufficiently exhibited, and if it exceeds 2 parts by mass, the antioxidant volatilizes 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 silica fine powder, a high molecular weight silicone resin or the like in order to adjust the viscosity. In particular, silica fine powder is more preferable because it can function not only as a thickening agent but also as a thixotropic agent, so that the fluidity of the curable resin composition of the present invention can be controlled.

  The average particle size of the silica fine powder is not particularly limited, but a preferred range is 0.1 to 100 nm, and a more preferred range is 1 to 50 nm. When it is used for encapsulating 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 does not pose a problem in applications such as a build-up board or the like, a wiring board such as a build-up board, or semiconductor encapsulation such as underfill that does not transmit light.

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

  The method for preparing the curable resin composition of the present invention is not particularly limited, and the components are put in a mixing machine such as a pot mill, a three-roll mill, a rotary mixer and a twin-screw mixer at a predetermined mixing ratio, and mixed. , Can be prepared.

  At the time of preparation, an organic solvent may be mixed if necessary, and after mixing until uniform, the solvent may be volatilized. The organic solvent used at this time 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, which are easy to remove, can be used. , THF, ethyl acetate and the like are preferably used. Strongly acidic ones such as acetic acid and basic ones such as triethylamine and pyridine react with glycidyl groups or reactive hydroxyl groups and are not preferred. Further, those having a high boiling point such as dimethylformamide and dimethylsulfoxide are not preferable because the residual solvent poses a problem. When a solvent is used, it is preferable to finally remove the solvent under reduced pressure to obtain a curable resin composition.

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

  The curable resin composition of the present invention can be thermoset. The thermosetting condition is usually 150 to 250 ° C. At temperatures lower than 150 ° C, curing does not proceed sufficiently, and at temperatures higher than 250 ° C, problems such as decomposition of the target product and volatilization of low molecular weight components occur, and there is also a demand for equipment used for curing. Get tougher. The heating time for curing can be in the range of 0.5 to 48 hours. This heating may be performed in multiple times. When a particularly high degree of curing is required, it is not preferable to cure at an excessively high temperature, and for example, the temperature may be gradually raised to proceed with the curing, and the final curing temperature may be set to 200 ° C. or lower. It is preferably 180 ° C or lower.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1: Synthesis of substrate (4,4 '-(dimethylmethylene) bis [2- (2-propenyl) phenyl diallyl ether]) In a 500 mL three-neck round bottom flask, 138 g (1 of potassium carbonate (Nippon Soda Co., Ltd.)) Solution of 0.000 mol) in pure water 125 g, 4,4 ′-(dimethylmethylene) bis [2- (2-propenyl) phenol] represented by the formula (7) (manufactured 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, the reactor was purged with nitrogen gas and heated to 85 ° C. Under a nitrogen gas stream, 220 g (2.19 mol) of allyl acetate (manufactured by Showa Denko KK), 2.62 g (10.0 mmol) of triphenylphosphine (manufactured by Kitako Chemical Co., Ltd.), and 50% water-containing 5% -Pd / After adding 84.6 mg (0.0200 mmol as Pd atomic weight) of C-STD type (manufactured by NE Chemcat Corporation), the temperature was raised to 105 ° C. in a nitrogen gas atmosphere and the reaction was carried out for 4 hours, and then allyl acetate 22. 0 g (0.219 mol) was added additionally, and heating was continued for 12 hours. After the 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) and then adding 200 g of toluene and maintaining the temperature at about 80 ° C. to confirm that no white precipitate was deposited, Pd / C was filtered (a membrane filter having a pore size of 1 micron). It was recovered by 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 water layer was separated. After confirming that the aqueous layer was neutral, the organic layer was separated and concentrated under reduced pressure to obtain 4,4 '-(dimethylmethylene) bis [2] represented by the formula (8). -. (2-propenyl) brown liquid whose main component is phenyl diallyl ether] (93.6 g, 241 mmol, 92.0% yield) of the brown liquid the ¹ H-NMR measurement result, equation (8 ) 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.}, δ1.66 (6H, s, CH ₃ ), δ3.39 (4H, d, PhC H ₂ CH═CH ₂ ), δ4.95-5.55. (4H, m, PhCH ₂ CH = C H ₂ ), δ 5.25 (2H, d, PhOCH ₂ CH = C H H), δ 5.42 (2H, d, PhOCH ₂ CH = CH H ), δ 5.25 _{(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) In a 200 mL three-neck round bottom flask, 4,4 ′-(dimethyl) obtained in Synthesis Example 1 above was used. Methylene) bis [2- (2-propenyl) phenyl diallyl ether] 18.1 g (46.5 mmol), sodium tungstate monohydrate (manufactured by Japan Inorganic Chemical Industry Co., Ltd.) 1.53 g (4.70 mmol), phosphorus 0.231 g (2.35 mmol) of acid (manufactured by Wako Pure Chemical Industries, Ltd.), 0.230 g (2.35 mmol) of sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.), and trioctylmethylammonium hydrogen sulfate (MTOAHS, Asahi) 2.17 g (4.70 mmol) manufactured by Kagaku Kogyo Co., Ltd. was added and dissolved in 18 g of toluene (manufactured by Junsei Chemical Co., Ltd.). After the temperature was raised to 65 ° C, 51.1 g (0.465 mol) of 35 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. The speed was 400 rpm). At the beginning of the reaction, the pH of the reaction solution was 1.5, and the pH of the reaction solution after the reaction for 2 hours was 3.7. After the reaction was completed, the reaction solution was cooled to room temperature, and then 20 g of water was added for liquid separation. The organic layer was separated, and 15 g of an aqueous sodium sulfite solution (10% by mass, manufactured by Wako Pure Chemical Industries, Ltd.) was added to wash the remaining hydrogen peroxide. The aqueous layer was removed, 20 g of water was added, and the mixture was washed again. By separating 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%) were obtained. The yield was calculated as (the amount of the mixture containing the desired epoxy compound after the above post-treatment / the amount of the substance obtained when the oxidation reaction proceeded at a reaction rate of 100%) × 100). Since the epoxy equivalent of the product is close to the theoretical epoxy equivalent of the compound represented by the formula (9), it is suggested 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. The measurement data belonging to the compound represented by the formula (9) are 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 (6 H, s, CH ₃ ), δ 2.54 (2 H, m, PhCH ₂ CHC H HO), δ 2.7-2.8 (6 H. , M, PhC H ₂ CHCHHO, PhCH ₂ CHCH H 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 having an allyl group at the ortho or para position (abbreviated as BRG-556-AL2)) Potassium carbonate (manufactured by Nippon Soda Co., Ltd.) in a 2000 mL three-necked flask. A solution prepared by dissolving 171.1 g (1.24 mol) in 155.6 g of pure water, a phenol novolac represented by formula (10) (SHONOL (registered trademark) BRG-556, o = 2 to 7) (Showa Denko KK 500.0 g (manufactured by the company) and 65.61 g (0.619 mol, solid) of sodium carbonate (manufactured by Kanto Kagaku Co., Ltd.) were charged, and the reactor was replaced with nitrogen gas and heated to 85 ° C. Under a nitrogen gas stream, 272.7 g (2.72 mol) of allyl acetate (manufactured by Showa Denko KK) and 3.247 g (1 of triphenylphosphine (manufactured by Kitako Chemical Co., Ltd.) 2.4 mmol), and 50% water content of 5% -Pd / C-STD type (manufactured by NE Chemcat Corporation) 0.105 g (0.0248 mmol as Pd atomic weight) were 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 which stirring was stopped and the mixture was allowed to stand and the organic layer and aqueous layer were separated. Separated into layers, pure water (200 g) was added until the precipitated salt was dissolved, 200 g of toluene was added, and the mixture was kept at a temperature of about 80 ° C. to confirm that a white precipitate was not deposited. Then, Pd / C was recovered by filtration (a membrane filter having a pore size of 1 micron (pressurized (0.3 MPa) using KST-142-JA manufactured by Advantech)). 100 g of this filter residue was collected. Along with washing, the aqueous layer was separated.The organic layer was washed twice with 200 g of water at about 50 ° C., and it was confirmed that the aqueous layer was neutral. An oily substance was obtained (560 g, quantitative). As a result of ¹ H-NMR measurement of this brown oily substance, a phenol novolac allyl ether compound represented by the formula (11) (hereinafter, abbreviated as BRG-556-AL) was obtained. It was confirmed that the compound was contained as a main component, and the measurement data belonging to the compound represented by the formula (11) are as follows.
^{1 H-NMR {400MHz, CDCl} 3, 27 ℃}, δ3.6-4.0 (4H, m, PhCH 2 Ph), δ4.4-4.8 (2H, m, C H 2 CH = CH 2 _{), δ5.1-5.3 (1H, m,} CH 2 CH = CH H), δ5.3-5.5 (1H, m, CH 2 CH = C H H), δ5.8-6.2 _{(1H, m, CH 2 C} H = CH 2), δ6.6-7.3 (12H, m, aromatic).

A magnetic stir bar and 500 g of the phenol novolac allyl ether product obtained in the above synthesis were put 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 a phenol novolac allyl substitution product (hereinafter, abbreviated as BRG-556-CL) represented by the formula (12) was contained as a main component. The measurement data belonging to the compound represented by the formula (12) are as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2 H, m, C H ₂ CH═CH ₂ ), δ 3.6-4.0 (5 H, m, PhCH ₂ Ph). , OH), δ 4.6-5.0 (1H, m, CH ₂ CH = CH H ), δ 5.0-5.3 (1H, m, CH ₂ CH = C H H), δ 5.8-6. _{.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 novolac allyl substitution product (BRG-556-CL) obtained in the above synthesis A phenol novolac type allyl ether having an allyl group at the ortho 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 this dark brown oily substance, a phenol novolac type allyl ether having an allyl group at the ortho position or the para position represented by the formula (13) (hereinafter, abbreviated as BRG-556-AL2) is a main component. Confirmed to include as. The measurement data belonging to the compound represented by the formula (13) are as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.4-4.0 (4 H, 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 having a glycidyl group at the ortho or para position (abbreviated as BRG-556-EP2) A 200 mL three-neck round bottom flask was charged with the ortho or para position obtained in the above Synthesis Example 3. 20 g (about 106 mmol) of phenol novolac type allyl ether having an allyl group at the position (BRG-556-AL2), sodium tungstate monohydrate 3.48 g (10.6 mmol), phosphoric acid 0.52 g (5.27 mmol) , 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 the temperature was raised to 70 ° C., 61.7 g (0.63 mol) of 35 mass% hydrogen peroxide aqueous solution was added dropwise with stirring over 1 hour, and the mixture was further stirred at 70 ° C. for 2 hours (stirring speed 400 rpm). At the beginning of the reaction, the pH of the reaction solution was 1.4, and the pH of the reaction solution after reacting for 2 hours was 3.4. After the reaction was completed, the reaction solution was cooled to room temperature, and then 20 g of water was added for liquid separation. The organic layer was separated, and 20 g of an aqueous sodium sulfite solution (10% by mass) was added to the organic layer for washing to reduce residual hydrogen peroxide. The aqueous layer was removed, 20 g of water was added, and the mixture was 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 highly viscous 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 the phenol novolac type polyvalent glycidyl compound represented by the formula (14) was contained as a main component. The phenol novolac-type polyvalent glycidyl compound represented by the formula (14) is a mixture of repeating units o of 2 to 7, but the epoxy equivalent is almost independent of the repeating units o and is substantially constant. 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 the formula (14) are as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
^{1 H-NMR {400MHz, CDCl} 3, 27 ℃}, δ2.5-2.8 (2H, m, PhOC H 2 CHCH 2 O), δ2.8-3.0 (4H, m, PhC H 2 CHCH _{2 O, PhCH 2 CHC H 2} O), δ3.1-3.4 (2H, m, PhOCH 2 CHC H 2 O), δ3.6-4.0 (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) having allyl group at ortho or para position) allyl ether (abbreviated as TRI-220-AL2) Shonor (registered trademark) as a raw material Except for using 500.0 g of triphenylmethane novolak (SHONOL (registered trademark) TRI-220, p = 2 to 7) (manufactured by Showa Denko KK) represented by the formula (15) instead of BRG-556. The substrate was synthesized in three steps in the same manner as BRG-556-AL2 of Synthesis Example 3. First, in the first step, a triphenylmethane novolac allyl ether compound (hereinafter abbreviated as TRI-220-AL) was synthesized and brown. 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 (2 H, m, PhCHPh), δ 4.5-4.6 (2 H, m, C H ₂ CH = CH ₂ ), _{δ5.2-5.3 (1H, m, CH 2} CH = CH H), δ5.3-5.5 (1H, m, CH 2 CH = C H H), δ6.0-6.1 (1H _{, m, CH 2 C H =} CH 2), δ6.6-7.3 (17H, m, aromatic).

Similar to the above-mentioned synthesis of BRG-556-AL2, a triphenylmethane novolac allyl-substituted product (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 this brown oily substance, it was confirmed that the compound represented by the formula (17) was contained as a main component. The measurement data belonging to the compound represented by the formula (17) are as follows.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ 3.2-3.4 (2 H, m, PhCHPh), δ 4.8-4.9 (1 H, m, CH H CH = CH ₂ ), δ 5 _{.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 the above BRG-556-AL2, triphenylmethane novolac 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 this brown oil, 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) are 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), δ5.0-5.4 (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 novolac (polycondensation product of phenol and benzaldehyde) glycidyl ether (abbreviated as TRI-220-EP2) having a glycidyl group in the ortho or para position, in a 200 mL three-neck round bottom flask, the above synthesis example 15 g (about 48 mmol) of triphenylmethane novolac-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 the temperature was raised to 70 ° C., 61.7 g (0.63 mol) of 35 mass% hydrogen peroxide aqueous solution was added dropwise with stirring over 1 hour, and the mixture was further stirred at 70 ° C. for 2 hours (stirring speed 400 rpm). At the beginning of the reaction, the pH of the reaction solution was 1.4, and the pH of the reaction solution after reacting for 2 hours was 3.4. After the reaction was completed, the reaction solution was cooled to room temperature, and then 20 g of water was added for liquid separation. The organic layer was separated, and 20 g of an aqueous sodium sulfite solution (10% by mass) was added to the organic layer for washing to reduce residual hydrogen peroxide. The aqueous layer was removed, 20 g of water was added, and the mixture was 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 = measured epoxy equivalent / theoretical epoxy equivalent) of 1.29. Was obtained (11.4 g, 36 mmol, yield 75.7%). As a result of ¹ H-NMR measurement of this brown highly viscous oil, it was confirmed that the triphenylmethane novolac-type polyvalent glycidyl compound represented by the formula (19) was contained as a main component. The triphenylmethane novolac-type polyvalent 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 irrespective of the repeating units p, and therefore p = The compound at 5 was used as a model skeleton, and the theoretical epoxy equivalent 143 at that time was used as Er. The measurement data belonging to the compound represented by the formula (19) are as follows. The ¹ H-NMR spectrum of the product is shown in FIG.
¹ H-NMR {400 MHz, CDCl ₃ , 27 ° C.}, δ2.4-2.6 (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), δ2.8-3.0 (2H, m, PhOCH 2 CHC H 2 O), δ3.0-3.3 (2H, m, PhCHPh), δ3.8- _{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 materials of the curable resin composition used for the characteristic evaluation of the cured product are 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 33 ppm, viscosity 18.5 mPa · 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 48 ppm, viscosity 168 mPa · 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 42 ppm, viscosity 242 mPa · s (150 ° C)
・ Epoxy resin 4
Commercially available bisphenol A type glycidyl compound JER828EL (manufactured by Mitsubishi Chemical Corporation)
Epoxy equivalent 191, total chlorine content 302 ppm, viscosity 12 mPa · s
・ Epoxy resin 5
Commercially available phenol novolac type glycidyl compound N740 (manufactured by DIC Corporation)
Epoxy equivalent 179, total chlorine content 1329 ppm, viscosity 54 mPa · s (150 ° C)
-Phenolic curing agent 1 (corresponding to the phenol curing agent (B) of the present invention)
Straight Novolac BRG-556 (Showa Denko KK)
Hydroxyl equivalent 103
-Phenolic curing agent 2 (corresponding to the phenol curing agent (B) of the present invention)
Phenol / salicylaldehyde polymerization type triphenylmethane novolac hydroxyl equivalent 111
Synthetic / phenolic curing agent 3 (corresponding to the phenolic curing agent (B) of the present invention) according to a generally known method (for example, described in JP 2012-193217 A).
Naphthol Novolac SN395 (Nippon Steel & Sumitomo Metal Corporation)
Hydroxyl equivalent 110
・ Phenolic curing agent 4
Cresol Novolac CRG-951 (Showa Denko KK)
Hydroxyl equivalent 118
・ Phenolic curing agent 5
Cresol / salicylic aldehyde polymerization type triphenylmethane novolac TRI-002 (manufactured by Showa Denko KK)
Hydroxyl equivalent 107
-Curing accelerator 1 (corresponding to the curing accelerator (C) of the present invention)
Commercially available triphenylphosphine (manufactured by Kitako 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 Co., Ltd.)

  The epoxy equivalent, total chlorine content, and viscosity of the epoxy resin, 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. After weighing 0.1 to 0.2 g of the sample and putting it in an Erlenmeyer flask, 10 mL of chloroform is added and dissolved. Next, 20 mL of acetic acid is added, and subsequently 10 mL of tetraethylammonium bromide acetic acid solution (tetraethylammonium bromide 100 g dissolved in 400 mL of acetic acid) is added. 4 to 6 drops of crystal violet indicator are added to the obtained solution and titrated with a 0.1 mol / L perchloric acid acetic acid solution, and the epoxy equivalent is calculated 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 (mL) of perchloric acid acetic acid solution consumed for titration up to the end point in the blank test
V ₁ : Amount of perchloric acid acetic acid solution consumed for titration until 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 IC-1000 manufactured by Dionex and IonPac AS12A (4 mm) column, and the eluent is measured as 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 (MSR301 manufactured by Anton Paar) and a cone plate (CP25-2 manufactured by Anton Paar, Part. No. 79039) under the following conditions.
Temperature: 150 ° C
Rotation speed: 0.1 rpm to 1000 rpm
Sample weight: about 0.2g

<Glass transition temperature (Tg)>
It is measured by thermomechanical measurement (TMA). Using a TMA / SS6100 thermomechanical analyzer manufactured by SII Nano Technology Co., Ltd., a test piece of 5 × 5 × 5 mm 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. Is used to measure. The glass transition temperature is defined as the temperature at the intersection of the extrapolation lines of two straight lines drawn before and after the inflection point based on the transition in the obtained expansion curve.

  The components shown in Table 1 were blended in the proportions shown in the table. "OH group / glycidyl group" in the table means the molar ratio of the hydroxyl group of the phenolic curing agent to the total of the glycidyl group and the glycidyl ether group of the epoxy resin (the number of moles of the hydroxyl group of the phenolic curing agent / [the glycidyl group of the 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 as described above was pulverized using an agate mortar. The powder was pulverized until the particle diameter of the powder became 1 mm or less.

  The obtained powder was molded into a plate-like cured product having a thickness of 5 mm using a heating press machine manufactured by Toyo Seiki Seisakusho Co., Ltd. The mold used was one in which the central portion of a Teflon (registered trademark) plate was cut into a square shape. After press molding at 150 ° C. and heat treatment at 150 ° C. for 1 hour as it was, post-curing was performed at 200 ° C. for 2 hours using an oven.

  The glass transition temperature (Tg) of the obtained cured product was measured. Table 1 shows the obtained physical property values. It is suggested that when a polyvalent glycidyl compound is used, it has a high Tg and good heat resistance as compared with general glycidyl compounds.

  When a cured product was prepared using the same phenolic curing agent, when a polyvalent glycidyl compound applied in the present invention was used, a general glycidyl compound having no glycidyl group at the ortho position of the glycidyl ether group was used. It is shown that it has high heat resistance (glass transition temperature Tg) as compared with the case. For example, in Example 1 in which a polyvalent glycidyl ether compound having bisphenol A as a basic skeleton (epoxy resin 1) was used, Tg was lower than that in Comparative Example 2 in which a normal glycidyl ether compound of bisphenol A (epoxy resin 4) was used. It improved by 87 ° C. Similarly, Example 2 using a polyvalent glycidyl ether having a basic skeleton of straight novolac (epoxy resin 2) 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 the phenol-based curing agent and the Tg of the obtained cured product is the same as when the polyvalent glycidyl compound (epoxy resin 1 to 3) applied to the curable resin composition of the present invention is used and when the general glycidyl compound is used. The tendency is different when the (epoxy resin 4, 5) is used. When a general glycidyl compound (epoxy resin 4, 5) is used, the heat resistance (Tg) tends to be higher when the curing agent (B) has a more rigid skeleton. The results are shown in Comparative Examples 2 and 3 when using the epoxy resin 4, and in Comparative Examples 5 and 6 when using the epoxy resin 5. 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 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 straight straight novolac is used. With respect to the epoxy resin 1, it can be seen from Example 1 and Comparative Example 1 that the Tg is 26 ° C. higher when the phenolic curing agent having less steric hindrance is used. Similarly, regarding Example 2 and Comparative Example 4 with respect to the epoxy resin 2, it can be seen that the Tg is 18 ° C. higher when the phenolic curing agent having less steric hindrance is used. Similarly, when a cresol / salicylaldehyde polymerized triphenylmethane novolak having a methyl group at the ortho position of a reactive functional group (hydroxy group) is used, a phenol / salicylaldehyde polymerized triphenylmethane novolak having no methyl group is used. Shows higher heat resistance (Tg) when used as a curing agent (comparison between Example 4 and Comparative Example 7). From these results, it is considered that since the functional group density of the polyvalent glycidyl compound is high, the reactivity decreases as the steric hindrance around the reactive group of the phenolic curing agent increases.

  Similarly, Examples 5 to 7 also show that a cured product having good heat resistance can be obtained by using various kinds of polyvalent glycidyl compounds applied to the present invention together with a phenol-based curing agent.

  The influence of the above steric hindrance was examined from the quantitative evaluation of the epoxy curing reaction. Specifically, the quantification was tried using the Kamal model formula (1) based on the Arrhenius formula. This model formula is, for example, Journal of Polymer Science, Part B Polymer Physics 2004, 42, 20, 3701-3712, SEI GAKKAI Vol 68. No. 4, 2012, etc., it is widely used in explaining the curing reaction of epoxy compounds. In this model formula, the reaction rate is calculated using the relationships 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 by setting the temperature rising rate from 100 ° C. to 250 ° C. to 5, 10, 20, 40 ° C./min, and the integrated value up to an arbitrary temperature T is divided by the integrated values of all peaks. Can be calculated. When dα / dT is plotted against α, a mountain curve is obtained. The mountain shape is formed because the reaction rate increases as the temperature rises, but when the crosslinking progresses to a certain extent, the control of the reaction shifts to the diffusion rate control and the reaction rate decreases. When the obtained graph is fitted using a spreadsheet software (for example, a solver function of EXCEL (registered trademark) software of Microsoft Corporation), each constant in the above mathematical expression 1 can be roughly estimated.

  The exothermic behavior of the curable resin composition of Example 1 was measured using DSC, and the chevron curve obtained by fitting it to the above model is shown in FIG. 4 as the measured value. Further, a mountain-shaped curve obtained as a result of fitting with the actual measurement value using the spreadsheet software is shown in FIG. 4 as the calculated value. Table 2 shows each constant of the mathematical expression (1) obtained from the result of fitting.

<Differential scanning calorimetry (DSC measurement)>
Using a Neztch DSC / differential scanning calorimeter, in an aluminum cell under the conditions of a temperature range of 30 ° C. to 250 ° C., a heating rate of 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.

The reaction rate constants K ₁ and K ₂ can be obtained by substituting the calculation results of the coefficients obtained by fitting into the Arrhenius equations (2) and (3). It is known that the influence of the resin on the reaction rate is reflected in the term of K ₂ . The value of K ₂ is 0.042 (the temperature is calculated at 150 ° C. (423 K)).

The above experiment and analysis were performed on Comparative Example 4 as well, and the reaction rate constant K ₂ was calculated to be 0.007. This value suggests that the reactivity of Comparative Example 4 is lower than that of Example 1.

  These results indicate that a methyl group is present at the ortho position of the reactive hydroxyl group as compared with the case where cresol novolac (CRG-951) having a methyl group at the ortho position of the reactive hydroxyl group of the phenolic curing agent is used as described above. The use of BRG-556 which does not have a higher reactivity supports the tendency that the heat resistance of the cured product becomes higher.

  By using the curable resin composition in which the polyhydric glycidyl compound of the present invention and a specific phenolic curing agent are used in combination, the crosslink density in the resin can be increased, and heat resistance, rigidity, and adhesiveness are excellent. A cured product can be obtained. Therefore, the curable resin composition of the present invention can be suitably used as a semiconductor encapsulant, particularly as a power semiconductor encapsulant requiring high heat resistance.

Claims (9)

Curing containing 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 curable resin composition contains only the compound represented by the general formula (1) as the polyvalent glycidyl compound (A), the epoxy equivalent of the compound is E, When the theoretical epoxy equivalent of the compound having a skeleton and all of R ¹ and R ² is a group represented by the formula (3) is Er, E / Er is 1.01 to 1.20, curability Resin composition.

(In the formula, R ¹ and R ² are each independently a group represented by the following formula (2) or (3), and Q is an alkylene group represented by the formula: —CR ³ R ⁴ —. And R ³ and R ⁴ are methyl groups, and n represents 0.)

(R ⁵ , R ⁶ and R ⁷ in the formula (2) represent hydrogen atoms, and R ⁸ , R ⁹ and R ¹⁰ in the formula (3) represent hydrogen atoms.)   The phenol-based curing agent (B) is any one of a phenol novolac resin, a phenol aralkyl resin, a naphthol aralkyl resin, a dicyclopentadiene / phenol polymerization resin, a benzaldehyde / phenol polymerization novolac resin, or a terpene / phenol polymerization resin. The curable resin composition according to claim 1.   The curable resin composition according to claim 2, wherein the phenol-based curing agent (B) is a phenol novolac resin.   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) (moles of hydroxyl groups in the phenolic curing agent (B) / [polyvalent glycidyl compound The total molar number of glycidyl groups and glycidyl ether groups of (A)] is 0.8 to 1.0, The curable resin composition according to any one of claims 1 to 3.   The curable resin composition according to any one of claims 1 to 4, further comprising a curing accelerator (C).   The curable resin composition according to claim 1, further comprising a filler (D).   7. The filler according to claim 6, 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 a mixture thereof. Curable resin composition.   The curable resin composition according to claim 7, which is for encapsulating a semiconductor.   The curable resin composition according to claim 1, wherein the E / Er is 1.05 or less.

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