WO2018173500A1 - Active ester composition - Google Patents

Abstract

Provided are: an active ester composition having high curability and exceptional properties such as dielectric properties, heat resistance, and moisture absorption resistance in the cured product; a cured product of the composition; and a semiconductor sealing material and a printed wiring board obtained using the composition. An active ester composition containing an active ester compound (A) and an acid anhydride (B) as essential components, the acid anhydride (B) having as an essential component a polyfunctional acid anhydride (B1) having two or more acid anhydride groups; a cured product of the composition; and a semiconductor sealing material and a printed wiring board obtained using the composition.

Description

Active ester composition

The present invention relates to an active ester composition having high curability and excellent properties such as dielectric properties, heat resistance and moisture absorption resistance in a cured product, the cured product, a semiconductor sealing material using the composition, and The present invention relates to a printed wiring board.

In the technical field of insulating materials used for semiconductors, multilayer printed boards, etc., development of new resin materials that meet these market trends is required as various electronic members become thinner and smaller. Specific required performance includes not only heat resistance and moisture absorption resistance in the cured product, but also measures to increase the signal speed and frequency, the dielectric constant and dielectric loss tangent value in the cured product are low, under high temperature conditions It is also important that there is no change in physical properties such as glass transition temperature (Tg) as reliability, and that a cure shrinkage rate and a linear expansion coefficient are low as countermeasures against warping and distortion accompanying thinning.

A technique using di (α-naphthyl) isophthalate as a curing agent for an epoxy resin is known as a resin material excellent in heat resistance, dielectric properties, copper foil adhesion, and the like in a cured product (see Patent Document 1 below). The epoxy resin composition described in Patent Document 1 uses di (α-naphthyl) isophthalate as an epoxy resin curing agent, thereby comparing with a case where a conventional epoxy resin curing agent such as a phenol novolac resin is used. The values of dielectric constant and dielectric loss tangent of cured products are certainly low, but they are low in curability and need to be cured at high temperature for a long time. Had a problem.

JP 2003-82063 A

Therefore, the problem to be solved by the present invention is an active ester composition having high curability and excellent performance such as dielectric properties, heat resistance and moisture absorption resistance in the cured product, the cured product, and the composition. The object is to provide a semiconductor sealing material and a printed wiring board to be used.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a polyfunctional acid anhydride containing an active esterified product and an acid anhydride and having two or more acid anhydride groups as the acid anhydride. The product was found to have high curability and excellent properties such as dielectric properties, heat resistance and moisture absorption resistance in the cured product, and the present invention was completed.

That is, the present invention contains an active ester compound (A) and an acid anhydride (B) as essential components, and the acid anhydride (B) has two or more acid anhydride groups. The present invention relates to an active ester composition containing (B1) as an essential component.

The present invention further relates to a curable composition containing the active ester composition and a curing agent.

The present invention further relates to a cured product of the curable composition.

The present invention further relates to a semiconductor sealing material using the curable composition.

The present invention further relates to a printed wiring board using the curable composition.

According to the present invention, an active ester composition having high curability and excellent properties such as dielectric properties, heat resistance, and moisture absorption resistance in a cured product, the cured product, and semiconductor encapsulation using the composition Materials and printed wiring boards can be provided.

Hereinafter, the present invention will be described in detail.
The active ester composition of the present invention contains an active ester compound (A) and an acid anhydride (B) as essential components, and the acid anhydride (B) has two or more acid anhydride groups. An acid anhydride (B1) is an essential component.

The active ester compound (A) is not particularly limited as long as it is a compound having an aromatic polyester structure in the molecular structure. The molecular weight is not particularly limited, and may be a single molecular weight compound or an oligomer or polymer having a molecular weight distribution. Specific examples of the active ester compound (A) include the following (A1) to (A4). These are merely examples of the active ester compound (A), and the active ester compound (A) of the present invention is not limited thereto. Moreover, an active ester compound (A) may be used individually by 1 type, and may use 2 or more types together.
Active ester compound (A1): esterified active ester compound (A2) of a compound (a1) having one phenolic hydroxyl group in the molecular structure and an aromatic polycarboxylic acid or its acid halide (a2): in the molecular structure An esterified active ester resin (A3) of a compound (a3) having two or more phenolic hydroxyl groups and an aromatic monocarboxylic acid or acid halide (a4) thereof: a compound having one phenolic hydroxyl group in the molecular structure (A1), an aromatic polycarboxylic acid or an acid halide thereof (a2) and an esterified active ester resin (A4) of a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure: an aromatic polycarboxylic acid or Its acid halide (a2), compound (a3) having two or more phenolic hydroxyl groups in the molecular structure, and fragrance Monocarboxylic acids or esters of the acid halide (a4)

Specific examples of the compound (a1) having one phenolic hydroxyl group in the molecular structure include phenol or a phenol compound having one or more substituents on the aromatic nucleus of phenol, naphthol or naphthol on the aromatic nucleus. Examples thereof include naphthol compounds having one or more substituents, anthracenol or anthracenol compounds having one or more substituents on the aromatic nucleus of anthracenol. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and a nonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural site in which the aromatic hydrocarbon group, the alkoxy group, the halogen atom, or the like is substituted on the aromatic nucleus. Examples of the aryloxy group include a phenyloxy group, a naphthyloxy group, an anthryloxy group, and a structural site in which the alkyl group, alkoxy group, halogen atom, or the like is substituted on the aromatic nucleus. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site in which the alkyl group, alkoxy group, halogen atom, or the like is substituted on the aromatic nucleus. As the compound (a1) having one phenolic hydroxyl group in the molecular structure, one type may be used alone, or two or more types may be used in combination.

Among these, a phenolic compound or a naphthol compound is preferable because a cured product excellent in various properties such as dielectric properties and heat resistance can be obtained. One or two of the above-described substituents on phenol, naphthol, or an aromatic nucleus thereof. Are more preferred. The substituent on the aromatic nucleus is preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aralkyl group.

Examples of the aromatic polycarboxylic acid or its acid halide (a2) include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid; benzenetricarboxylic acids such as trimellitic acid; naphthalene-1,4-dicarboxylic acid and naphthalene-2 , 3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene dicarboxylic acid such as naphthalene-2,7-dicarboxylic acid; acid halides thereof; having one or more substituents on the aromatic nucleus Compounds and the like. Examples of the acid halide include acid chlorides, acid bromides, acid fluorides, and acid iodides. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples thereof are as described above. The aromatic polycarboxylic acid or its acid halide (a2) may be used alone or in combination of two or more. Among these, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid or acid halides thereof are preferable because a cured product excellent in various properties such as dielectric properties and heat resistance can be obtained.

The compound (a3) having two or more phenolic hydroxyl groups in the molecular structure is, for example, various aromatic polyhydroxy compounds or one or more compounds (a1) having one phenolic hydroxyl group in the molecular structure. A novolac resin using a seed as a reaction raw material, one or more compounds (a1) having one phenolic hydroxyl group in the molecular structure, and the following structural formulas (x-1) to (x-5)

［式中ｈは０又は１である。Ｒ^１はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アリールオキシ基、アラルキル基の何れかであり、ｉは０又は１～４の整数である。Ｚはビニル基、ハロメチル基、ヒドロキシメチル基、アルキルオキシメチル基の何れかである。Ｙは炭素原子数１～４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは１～４の整数である。］
の何れかで表される化合物（ｘ）とを必須の反応原料とする反応生成物等が挙げられる。

[In the formula, h is 0 or 1. R ¹ is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, and i is an integer of 0 or 1 to 4. Z is any one of a vinyl group, a halomethyl group, a hydroxymethyl group, and an alkyloxymethyl group. Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group. j is an integer of 1 to 4. ]
Or a reaction product using the compound (x) represented by any of the above as an essential reaction raw material.

Examples of the various aromatic polyhydroxy compounds include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl. In addition to bisphenol and the like, compounds having one or more substituents on these aromatic nuclei can be mentioned. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples thereof are as described above.

Specific examples of the aliphatic hydrocarbon group, alkoxy group, halogen atom, aryl group, aryloxy group and aralkyl group for R ¹ in the structural formulas (x-1) to (x-5) are as described above. . The reaction between the compound (a1) having one phenolic hydroxyl group in the molecular structure and the compound (x) is carried out by heating and stirring under acid catalyst conditions and at a temperature of about 80 to 180 ° C. be able to.

The compound (a3) having two or more phenolic hydroxyl groups in the molecular structure may be used alone or in combination of two or more. Among them, the aromatic dihydroxy compound is preferably dihydroxynaphthalene or a compound having a substituent on the aromatic nucleus, and more preferably dihydroxynaphthalene having an aralkyl group because of excellent balance between curability and various performances in the cured product. Examples of the novolak type resin using one or more kinds of the compound (a1) as a reaction raw material include phenol, naphthol or an aliphatic hydrocarbon group having 1 to 6 carbon atoms or aralkyl on the aromatic nucleus as the compound (a1). A novolak resin using a compound having 1 to 2 groups is preferred. Examples of the reaction product comprising the compound (a1) and the compound (x) as essential reaction raw materials include phenol, naphthol or aliphatic groups having 1 to 6 carbon atoms on the aromatic nucleus as the compound (a1). A compound having one or two hydrocarbon groups or aralkyl groups and a compound represented by any of (x-1) to (x-4) as the compound (x) is preferable. .

The aromatic monocarboxylic acid or its acid halide (a4) is, for example, benzoic acid or benzoyl halide, the alkyl group, alkoxy group, halogen atom, aryl group, aryloxy group, aralkyl group on the aromatic nucleus. And the like are substituted. These may be used alone or in combination of two or more.

The active ester compound (A) can be produced, for example, by a method in which each reaction raw material is mixed and stirred under a temperature condition of about 40 to 65 ° C. in the presence of an alkali catalyst. You may perform reaction in an organic solvent as needed. Further, after completion of the reaction, the reaction product may be purified by washing with water or reprecipitation.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Further, it may be used as an aqueous solution of about 3.0 to 30%. Among these, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; and carbitols such as cellosolve and butyl carbitol. Examples include solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or as a mixed solvent of two or more.

The reaction ratio of each reaction raw material is appropriately adjusted according to the desired physical properties of the obtained active ester compound (A), and is particularly preferably as follows.

In the production of the active ester compound (A1), the reaction ratio between the compound (a1) having one phenolic hydroxyl group in the molecular structure and the aromatic polycarboxylic acid or its acid halide (a2) is as follows. Since the active ester compound (A1) can be obtained in a high yield, the total amount of carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or acid halide (a2) is 1 mol in the molecular structure. The proportion of the compound (a1) having one phenolic hydroxyl group is preferably 0.95 to 1.05 mol.

In the production of the active ester compound (A2), the reaction between the compound (a3) having two or more phenolic hydroxyl groups in the molecular structure and the esterified product of the aromatic monocarboxylic acid or its acid halide (a4) Since the target active ester compound (A2) can be obtained in a high yield, the ratio is based on a total of 1 mol of phenolic hydroxyl groups in the compound (a3) having two or more phenolic hydroxyl groups in the molecular structure. The aromatic monocarboxylic acid or its acid halide (a4) is preferably in a proportion of 0.95 to 1.05 mol.

In the production of the active ester resin (A3), the compound (a1) having one phenolic hydroxyl group in the molecular structure, the aromatic polycarboxylic acid or its acid halide (a2), and phenolic in the molecular structure The reaction ratio of the compound (a3) having two or more hydroxyl groups is such that the number of moles of the hydroxyl group of the compound (a1) having one phenolic hydroxyl group in the molecular structure and two or more phenolic hydroxyl groups in the molecular structure. The ratio of the compound (a3) to the number of moles of the hydroxyl group possessed is preferably 10/90 to 75/25, more preferably 20/80 to 60/40. In addition, the compound (a1) having one phenolic hydroxyl group in the molecular structure and the molecule with respect to 1 mol in total of the carboxyl group or acid halide group of the aromatic polycarboxylic acid or acid halide (a2) thereof The total number of hydroxyl groups possessed by the compound (a3) having two or more phenolic hydroxyl groups in the structure is preferably in the range of 0.9 to 1.1 mol.

In the production of the active ester compound (A3), depending on the reaction ratio of each raw material, the compound (a1) having one phenolic hydroxyl group in the molecular structure and the aromatic polycarboxylic acid or its acid halide (a2) A part of the active ester compound (A1) which is an esterified product may be formed. In this case, the content is preferably less than 40% in the ester compound (A3), more preferably in the range of 0.5 to 30%.

The content of the active ester compound (A1) in the active ester compound (A3) is a value calculated from the area ratio of the GPC chart measured under the following conditions.

Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ “TSK-GEL G4000HXL” manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids, filtered through a microfilter (50 μl)

In the production of the active ester compound (A4), the aromatic polycarboxylic acid or its acid halide (a2), the compound (a3) having two or more phenolic hydroxyl groups in the molecular structure, and the aromatic monocarboxylic acid Alternatively, the reaction ratio of the acid halide (a4) may be the aromatic polycarboxylic acid or the acid polycarboxylic acid or the acid halide (a4) with respect to 1 mol in total of the carboxyl group or acid halide group of the aromatic monocarboxylic acid or the acid halide (a4) The ratio of the acid halide (a2) to the total of carboxyl groups or acid halide groups is preferably in the range of 0.5 to 5 mol, more preferably in the range of 0.8 to 3 mol. Moreover, the aromatic polycarboxylic acid or its acid halide (a2) and the aromatic monocarboxylic acid or the same per 1 mol of the hydroxyl group of the compound (a3) having two or more phenolic hydroxyl groups in the molecular structure. The total of carboxyl groups or acid halide groups possessed by the acid halide (a4) is preferably in the range of 0.9 to 1.1.

The active ester compounds (A1) and (A2) preferably have a melt viscosity at 150 ° C. in the range of 0.01 to 5 dPa · s. In the present invention, the melt viscosity at 150 ° C. is a value measured with an ICI viscometer in accordance with ASTM D4287.

The active ester resins (A3) and (A4) preferably have a softening point measured in accordance with JIS K7234 in the range of 80 to 200 ° C, more preferably in the range of 85 to 180 ° C. In addition, the functional group equivalent is preferably in the range of 150 to 350 g / equivalent because of excellent balance between curability and various performances in the cured product. In the present invention, the functional group in the active ester resin means an ester bond site and a phenolic hydroxyl group in the active ester resin. The functional group equivalent of the active ester resin is a value calculated from the charged amount of the reaction raw material.

The acid anhydride (B) is not particularly limited as long as the acid anhydride (B) is a compound having one or more acid anhydride groups in the molecular structure, and a wide variety of compounds can be used. In the present invention, the acid anhydride group means a structural moiety represented by the following structural formula (3).

The acid anhydride (B) may be a monomolecular compound or an oligomer or polymer having a molecular weight distribution. In the present invention, any of monomolecular compounds, oligomers, and polymers may be used. For the purpose of reducing the viscosity of the composition, it is preferable to use monomolecular compounds, and the toughness and flexibility of the cured product are increased. For these purposes, oligomers or polymers are preferred.

In the present invention, a polyfunctional acid anhydride (B1) having two or more acid anhydride groups is used as the acid anhydride (B). As described above, the polyfunctional acid anhydride (B1) may be a monomolecular compound or an oligomer or polymer having a molecular weight distribution. Especially, since it becomes an active ester composition which can reduce a composition viscosity and is excellent in various physical properties in hardened | cured material, it is preferable to use a monomolecular compound as said polyfunctional acid anhydride (B1). In particular, the proportion of the monomolecular compound in the polyfunctional acid anhydride (B1) is preferably 50% by mass or more, and more preferably 80% by mass or more.

Among the polyfunctional acid anhydrides (B1), examples of monomolecular compounds include those represented by the following structural formula (4) in addition to benzenetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, and the like. And the like. Examples of the oligomer or polymer in the polyfunctional acid anhydride (B1) include a copolymer of styrene and maleic anhydride.

［式中Ｖは下記構造式（Ｖ－１）～（Ｖ－７）の何れかで表される構造部位であり、Ｗは直接結合又は２価の連結基である。式中２つのＶはそれぞれ同一であってもよいし、異なっていてもよい。

[Wherein V is a structural moiety represented by any of the following structural formulas (V-1) to (V-7), and W is a direct bond or a divalent linking group. In the formula, two Vs may be the same or different.

｛式中Ｒ^２はＷとの結合点或いはそれぞれ独立して水素原子、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、アラルキル基、ハロゲン原子の何れかである。構造式（Ｖ－２）及び構造式（Ｖ－５）中の酸無水物基の位置は固定されず、異性体であってもよい。｝］

{Wherein R ² is a bonding point with W or each independently a hydrogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an aralkyl group, or a halogen atom. The position of the acid anhydride group in Structural Formula (V-2) and Structural Formula (V-5) is not fixed and may be an isomer. }]

Specific examples of R ² include those exemplified as R ¹ in the structural formulas (x-1) to (x-5).

W in the structural formula (4) is a direct bond or a divalent linking group, and its specific structure is not particularly limited and can be appropriately selected according to the desired cured product performance and the like. Examples of the divalent linking group include, for example, a linear or branched alkylene group, a carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, an ester bond, and a structural site formed by a combination thereof. Examples of compounds in which W is a structural moiety containing an ester bond include, for example, one or more of R ^{3 in} the compounds represented by the following structural formulas (v-1) to (v-7) being a carboxy group Examples thereof include those obtained by reacting a certain compound with various polyol compounds or alkyl esterified products thereof in an arbitrary ratio. Examples of the polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyols such as biphenol and bisphenol. Compound: (Poly) oxyalkylene modified by introducing a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, (poly) oxypropylene chain, (poly) oxytetramethylene chain) into the molecular structure of the various polyol compounds. Examples include the body.

｛式中Ｒ^３はそれぞれ独立して水素原子、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、アラルキル基、ハロゲン原子、カルボキシ基の何れかである。構造式（ｖ－２）及び構造式（ｖ－５）中の酸無水物基の位置は固定されず、異性体であってもよい。｝］

{In the formula, each R ³ is independently a hydrogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an aralkyl group, a halogen atom, or a carboxy group. The position of the acid anhydride group in the structural formulas (v-2) and (v-5) is not fixed and may be an isomer. }]

Among the compounds represented by the structural formula (4), V is an active ester composition having excellent physical properties such as dielectric properties, heat resistance, and moisture absorption resistance in a cured product. Therefore, V represents the structural formula (V-1). To (V-4) are preferred, and those represented by any of the following structural formulas (4-1) to (4-6) are particularly preferred.

（式中Ｒ^２はそれぞれ独立して水素原子、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、アラルキル基、ハロゲン原子の何れかである。Ｒ^４は炭素原子数１～６の脂肪族炭化水素基である。ｍは０、１又は２、ｎは２～４の整数であり、ｍ＋ｎは２～４の整数である。）

(In the formula, each R ² is independently a hydrogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an aralkyl group, or a halogen atom. R ⁴ is an aliphatic group having 1 to 6 carbon atoms. A hydrocarbon group, m is 0, 1 or 2, n is an integer of 2 to 4, and m + n is an integer of 2 to 4.)

In the present invention, as the acid anhydride (B), a monofunctional acid anhydride (B2) having one acid anhydride may be used in combination with the polyfunctional acid anhydride (B1). In the monofunctional acid anhydride (B2), for example, in the structural formulas (v-1) to (v-7), R ³ is a hydrogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an aralkyl group, Examples thereof include compounds that are any of halogen atoms. When the monofunctional acid anhydride (B2) is used in combination, the effect of the present invention is sufficiently exerted, so the ratio of the polyfunctional acid anhydride (B1) in the acid anhydride (B) is It is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

The acid anhydride (B) preferably has a melting point of 250 ° C. or lower, more preferably in the range of 130 to 240 ° C.

These acid anhydrides (B) can also be obtained as commercial products. Examples of commercially available products include the Rikacid series from Shin Nippon Rika Co., Ltd. and the EPICLON series from DIC Corporation.

In the active ester composition of the present invention, the blending ratio of the active ester compound (A) and the acid anhydride (B) is appropriately adjusted according to the desired curability and physical properties of the cured product. It is preferable that the acid anhydride (B) is contained in the range of 0.1 to 500 parts by mass with respect to 100 parts by mass of the active ester compound (A) because of excellent balance between curability and physical properties of the cured product. More preferably, it is contained in the range of 10 to 400 parts by mass.

The curable composition of the present invention contains the active ester composition and a curing agent. The curing agent may be any compound that can react with the active ester composition of the present invention, and various compounds can be used without any particular limitation. An example of the curing agent is an epoxy resin. Examples of the epoxy resin include polyglycidyl ether of a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure.

In the curable composition of the present invention, the blending ratio of the active ester composition and the curing agent is not particularly limited and can be appropriately adjusted according to the desired cured product performance and the like. As an example of the blending in the case of using an epoxy resin as a curing agent, the total of functional groups in the active ester composition is 0.7 to 1.5 mol with respect to the total of 1 mol of epoxy groups in the epoxy resin. The ratio is preferably In the present invention, the functional group in the active ester composition means an ester bond site and an acid anhydride group in the active ester composition. The functional group equivalent of the active ester composition is a value calculated from the charged amount of reaction raw materials. Moreover, 1 mol of acid anhydride groups is calculated as one functional group.

The curable composition of the present invention may further contain a curing accelerator. Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, amine complex salts, and the like. Of these, triphenylphosphine for phosphorus compounds and 1,8-diazabicyclo- [5.4.0] -undecene (DBU) for tertiary amines are preferred because of their excellent curability, heat resistance, dielectric properties, and moisture absorption resistance. ), 2-ethyl-4-methylimidazole is preferred for imidazole compounds, and 4-dimethylaminopyridine and 2-phenylimidazole are preferred for pyridine compounds. The addition amount of these curing accelerators is preferably in the range of 0.01 to 15% by mass in 100 parts by mass of the curable composition.

The curable composition of the present invention may further contain other resin components. Other resin components include, for example, a phenolic hydroxyl group-containing compound such as a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure; diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, Amine compounds such as imidazole, BF ₃ -amine complexes, guanidine derivatives; amide compounds such as polyamide resins synthesized from dimers of dicyandiamide and linolenic acid and ethylenediamine; benzoxazine compounds; cyanate ester resins; bismaleimides Resin; Styrene-maleic anhydride resin; Allyl group-containing resin represented by diallyl bisphenol and triallyl isocyanurate; Polyphosphate ester and phosphate ester-carbonate copolymer . These may be used alone or in combination of two or more.

The mixing ratio of these other resin components is not particularly limited and can be appropriately adjusted according to the desired performance of the cured product. As an example of the blending ratio, it is preferably used in the range of 1 to 50% by mass in the curable composition of the present invention.

The curable composition of the present invention may contain various additives such as a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

The flame retardant is, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphate ester compound, phosphonic acid Compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) Cyclic organic phosphorus such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Compound and its compound such as epoxy resin and phenol resin Organophosphorus compounds such as derivatives reacted with nitrogen; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazines; silicone-based flame retardants such as silicone oil, silicone rubber and silicone resin; metal hydroxides; Examples include inorganic flame retardants such as metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, the content is preferably in the range of 0.1 to 20% by mass in the curable composition.

The inorganic filler is blended, for example, when the curable composition of the present invention is used for a semiconductor sealing material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially, since it becomes possible to mix | blend more inorganic fillers, the said fused silica is preferable. The fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the curable composition, a spherical one is mainly used. It is preferable. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable composition.

In addition, when the curable composition of the present invention is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

The active ester composition of the present invention and a curable composition using the active ester composition are highly curable and have excellent characteristics such as dielectric properties, heat resistance and moisture absorption resistance. In addition, the general required performance required for resin materials, such as solubility in general-purpose organic solvents and storage stability, is sufficiently high. Accordingly, it can be widely used for applications such as paints, adhesives, and molded products in addition to electronic materials such as semiconductor sealing materials, printed wiring boards, and resist materials.

In general, when the curable composition of the present invention is used for a semiconductor sealing material, it is preferable to blend an inorganic filler. The semiconductor sealing material can be prepared by mixing the compound using, for example, an extruder, a kneader, a roll, or the like. A method for molding a semiconductor package using the obtained semiconductor sealing material includes, for example, molding the semiconductor sealing material using a casting or transfer molding machine, injection molding machine, etc., and further a temperature of 50 to 200 ° C. Examples of the method include heating for 2 to 10 hours under conditions, and by such a method, a semiconductor device which is a molded product can be obtained.

When the curable composition of the present invention is used for a printed wiring board or a build-up adhesive film, it is generally preferable to mix and dilute an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. The type and blending amount of the organic solvent can be adjusted as appropriate according to the environment in which the curable composition is used. For example, for printed wiring board applications, the solvent must be a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethylformamide. The non-volatile content is preferably 40 to 80% by mass. For build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitols such as cellosolve, butyl carbitol, etc. It is preferable to use a solvent, an aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and it is preferable to use them in a proportion that the nonvolatile content is 30 to 60% by mass.

Moreover, the method of manufacturing a printed wiring board using the curable composition of the present invention includes, for example, impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg, and heating this with a copper foil. The method of making it crimp is mentioned. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnation amount of the curable composition is not particularly limited, but it is usually preferable to prepare so that the resin content in the prepreg is 20 to 60% by mass.

Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

The GPC measurement conditions in this example are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ “TSK-GEL G4000HXL” manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “GPC-8020 model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids, filtered through a microfilter (50 μl)

Production Example 1 Production of Active Ester Resin (A3-1) An addition reaction product of dicyclopentadiene and phenol (hydroxyl equivalent 165 g / equivalent) to a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer , 165 g of softening point 85 ° C.), 144 g of 1-naphthol, and 1315 g of toluene were dissolved in the system while substituting with nitrogen under reduced pressure. Next, 200 g of isophthalic acid chloride was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While performing nitrogen gas purge, the inside of the system was controlled to 60 ° C. or lower, and 434 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain an active ester compound (A3-1). The functional group equivalent of the active ester compound (A1-1) was 219 g / equivalent, and the softening point measured according to JIS K7234 was 130 ° C.

Production Example 2 Production of Active Ester Resin (A3-2) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 234.3 g of paratertiary butylphenol, 52.8 g of toluene, 37% by mass A formalin aqueous solution (52.8 g) and 49% sodium hydroxide (4.8 g) were charged. The mixture was heated to 75 ° C. with stirring, and stirred at the same temperature for 1 hour to react. After completion of the reaction, 7.1 g of primary sodium phosphate was added for neutralization, 363.2 g of toluene was added, and the mixture was washed 3 times with 121.1 g of water. It dried on heating pressure reduction conditions, and obtained 234.8 mass parts of intermediate bodies (1) containing unreacted para tertiary butyl phenol and a phenol resin. The hydroxyl equivalent of intermediate (1) was 155 g / equivalent.

A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 141.4 g of isophthalic acid chloride and 1000 g of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. 217 g of the intermediate (1) obtained above was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. Tetrabutylammonium bromide (0.4 g) was dissolved, the inside of the system was controlled to 60 ° C. or lower while performing nitrogen gas purge, and 280 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding 307.3 g of water to the organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then dried under heating under reduced pressure to obtain 298.1 g of an active ester resin (A3-2). The functional group equivalent of the active ester resin (A3-2) was 220 g / equivalent, and the softening point measured according to JIS K7234 was 132 ° C. Further, the content of bis (paratertiary butylphenyl) isophthalate in the active ester resin (A3-2) calculated from the GPC chart was 10.1%.

Production Example 3 Production of Active Ester Resin (A3-3) A flask equipped with a thermometer, cooling tube, fractionation tube, and stirrer was charged with 565 g of phenol and 106 g of benzaldehyde, and dissolved by stirring the system while substituting with reduced-pressure nitrogen. I let you. Next, 5.7 g of paratoluenesulfonic acid was charged and reacted at 135 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to 100 ° C., neutralized with an aqueous sodium hydroxide solution, and then the residual phenol was removed at 170 ° C. to obtain an intermediate (2). The hydroxyl group equivalent of the intermediate (2) was 150 g / equivalent.

A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 225 g of the intermediate (2), 102 g of isophthalic acid chloride, 70 g of benzoyl chloride, and 1000 g of toluene, and the inside of the flask was purged with nitrogen under reduced pressure. The solution was dissolved while stirring. While adding 0.5 g of tetrabutylammonium bromide and performing a nitrogen gas purge, the inside of the system was controlled to 60 ° C. or lower, and 327 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for another hour. After completion of the reaction, the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. The remaining toluene phase was charged with 340 g of water, stirred and mixed for about 15 minutes, and allowed to stand for liquid separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer became 7, and then dried under heating and reduced pressure to obtain 340 g of an active ester resin (A3-3). The functional group equivalent of the active ester resin (A3-3) was 228 g / equivalent, and the softening point measured according to JIS K7234 was 139 ° C.

Production Example 4 Production of Active Ester Compound (A1-1) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 202.0 g of isophthalic acid chloride and 1250 g of toluene. Dissolved with replacement. Next, 288.0 g of 1-naphthol was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.63 g of tetrabutylammonium bromide and carrying out nitrogen gas purge, the inside of the system was controlled to 60 ° C. or lower, and 400 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then dried under heating under reduced pressure to obtain an active ester compound (A1-1). The melt viscosity of the active active ester compound (A1-1) was 0.6 dPa · s.

Production Example 5 Production of Active Ester Compound (A1-2) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 202.0 g of isophthalic acid chloride and 1400 g of toluene, and the system was under reduced pressure nitrogen Dissolved with replacement. Next, 340.0 g of orthophenylphenol was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.70 g of tetrabutylammonium bromide and performing nitrogen gas purge, the inside of the system was controlled to 60 ° C. or lower, and 400 g of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then dried under heating and reduced pressure to obtain an active ester compound (A1-2). The melt viscosity of the active ester compound (A1-2) is 0.2 dP. s.

Production Example 6 Production of polyfunctional acid anhydride (B1-1) A flask equipped with a condenser, fractionator, and stirrer was charged with 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride (hereinafter referred to as PMMA). 458 g) and 542 g maleic anhydride were charged. The mixture was heated to 200 ° C. and stirred for 4 hours. While maintaining the temperature at 200 ° C., the pressure in the system was reduced to 10 mmHg to recover unreacted raw materials. To 215 g of the crude product remaining in the reaction vessel, 600 g of methyl isobutyl ketone was added and dissolved by heating to 110 ° C., followed by cooling to room temperature for crystallization. The obtained crystals were air-dried at room temperature to obtain 123 g of the desired polyfunctional acid anhydride (B1-1). The melting point of the polyfunctional acid anhydride (B1-1) was 168 ° C.

In addition, each compound used in the Examples and Comparative Examples of the present application is as follows.
Multifunctional acid anhydride (B1-2): “Benzophenone tetracarboxylic dianhydride [BTDA]” manufactured by Daicel Corporation, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, monofunctional acid Anhydride (B2-1): “Ricacid MH-700” manufactured by Shin Nippon Rika Co., Ltd., 7/3 (mass ratio) mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride / epoxy resin (1): “HP-7200H” manufactured by DIC Corporation, dicyclopentadiene type epoxy resin, epoxy group equivalent is 275 g / equivalent / epoxy resin (2): “N-655-EXP-S” manufactured by DIC Corporation, cresol novolac type epoxy resin The epoxy group equivalent is 202 g / equivalent

Examples 1 to 3 and Comparative Example 1
The curable composition was adjusted in the following manner, and various evaluation tests were performed. The results are shown in Table 1.

Production of Curable Composition (1) An active ester resin and an acid anhydride were charged into the flask in the proportions shown in Table 1 below, and heated to 170 ° C. and stirred while blowing nitrogen. After cooling to 150 ° C., an epoxy resin and dimethylaminopyridine were further blended and mixed to obtain a curable composition (1). The addition amount of dimethylaminopyridine was 0.5% by mass relative to the total mass of the active ester compound, acid anhydride, and epoxy resin.

Measurement of Glass Transition Temperature (Tg) The curable composition (1) was put into a mold and molded at 150 ° C. for 10 minutes using a press. The molded product was taken out from the mold and further cured at 175 ° C. for 5 hours. The molded product after curing was cut into a size of 5 mm × 54 mm × 2.4 mm and used as a test piece.
Using a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Ltd.), heating was performed from room temperature to 280 ° C. under the conditions of a rectangular tension method, a frequency of 1 Hz, and a temperature rising temperature of 3 ° C./min. The temperature at which the change in elastic modulus was maximum (tan δ was the largest) was evaluated as the glass transition temperature.

Evaluation of Curability After the test piece after the previous glass transition temperature (Tg) measurement was cooled to room temperature, the glass transition temperature (Tg) was measured again. The difference (ΔTg) between the measured value of the first glass transition temperature (Tg) and the measured value of the second glass transition temperature (Tg) was calculated and evaluated according to the following criteria. It is considered that the larger the ΔTg value, the lower the curability, and the more functional groups that did not react during molding remained.
A: ΔTg is 5 ° C. or less.
B: ΔTg exceeds 5 ° C

Measurement of dielectric constant and dielectric loss tangent A test piece was prepared using the same apparatus and conditions as those for the previous glass transition temperature (Tg) measurement. Test specimens stored for 24 hours in a room at 23 ° C and 50% humidity after heating and vacuum drying are compliant with JIS-C-6481, using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, at 1 GHz. The dielectric constant and dielectric loss tangent of were measured.

Production of Curable Composition (2) An active ester resin, an acid anhydride, and an epoxy resin were charged into a flask in the proportions shown in Table 1 below. Methyl ethyl ketone was added to 40% by weight of the total, and the mixture was stirred while blowing nitrogen. An appropriate amount of dimethylaminopyridine was added so that the gel time was 5 to 7 minutes to obtain a curable composition (2).

Evaluation of finger touch of prepreg A prepreg was prepared using the curable composition (2) under the following conditions. The touch of the obtained prepreg was evaluated. If the prepreg is sticky or tacky, the workability during processing and the storage stability of the prepreg will decrease.
A: No stickiness or tackiness B: Stickiness or tackiness (prepreg creation conditions)
Base material: Nitto Boseki Co., Ltd. glass cloth “# 2116” (210 × 280 mm)
Drying conditions: Dry at 160 ° C for 3 minutes

Evaluation of moisture absorption resistance A laminate was prepared using the curable composition (2) under the following conditions. The laminate was left in an atmosphere of 85 ° C. and 85% RH for 168 hours to perform a moisture absorption test. The laminate after the moisture absorption test was soaked in a molten solder bath for 10 seconds, A having no change in appearance, and B in which the formation of voids was observed was evaluated as B.
(Lamination board creation conditions)
Base material: Nitto Boseki Co., Ltd. glass cloth “# 2116” (210 × 280 mm)
Copper foil: “JTC foil” (18 μm) manufactured by JX Nippon Mining & Metals
Number of plies: 6
Prepregation conditions: 160 ° C
Curing conditions: 200 ° C., 40 kg / cm ² for 1.5 hours Molded plate thickness: 0.8 mm

Examples 4 to 6 and Comparative Example 2
The curable composition was adjusted in the following manner, and various evaluation tests were performed. The results are shown in Table 2.

Production of Curable Composition (3) The active ester compound and the acid anhydride were charged into the flask in the proportions shown in Table 2 below, and the mixture was heated to 170 ° C. and stirred while blowing nitrogen. After cooling to 150 ° C., other components were blended and mixed to obtain a curable composition (3).

Evaluation of finger touch of curable composition Touch evaluation of the curable composition (3) was performed under normal temperature conditions.
A: No stickiness or tackiness B: Stickiness or tackiness

Measurement of Glass Transition Temperature (Tg) The curable composition (3) was put into a mold and molded at 150 ° C. for 10 minutes using a press. The molded product was taken out from the mold and further cured at 175 ° C. for 5 hours. The molded product after curing was cut into a size of 5 mm × 54 mm × 2.4 mm and used as a test piece.
Using a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Ltd.), heating was performed from room temperature to 280 ° C. under the conditions of a rectangular tension method, a frequency of 1 Hz, and a temperature rising temperature of 3 ° C./min. The temperature at which the change in elastic modulus was maximum (tan δ was the largest) was evaluated as the glass transition temperature.

Evaluation of Curability After the test piece after the previous glass transition temperature (Tg) measurement was cooled to room temperature, the glass transition temperature (Tg) was measured again. The difference (ΔTg) between the measured value of the first glass transition temperature (Tg) and the measured value of the second glass transition temperature (Tg) was calculated and evaluated according to the following criteria. It is considered that the larger the ΔTg value, the lower the curability, and the more functional groups that did not react during molding remained.
A: ΔTg is 5 ° C. or less.
B: ΔTg exceeds 5 ° C

Production of Curable Composition (4) The active ester compound and the acid anhydride were charged into the flask in the proportions shown in Table 2 below, and the mixture was heated to 170 ° C. and stirred while blowing nitrogen. After cooling to 150 ° C., an epoxy resin and dimethylaminopyridine were blended and mixed to obtain a curable composition (4).

Measurement of dielectric constant and dielectric loss tangent Using the curable composition (4), a test piece was prepared in the same manner as the evaluation of curability. Test specimens stored for 24 hours in a room at 23 ° C and 50% humidity after heating and vacuum drying are compliant with JIS-C-6481, using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, at 1 GHz. The dielectric constant and dielectric loss tangent of were measured.

Claims (9)

An active ester compound (A) and an acid anhydride (B) are contained as essential components, and the acid anhydride (B) has a polyfunctional acid anhydride (B1) having two or more acid anhydride groups as essential components. An active ester composition. The active ester composition according to claim 1, wherein the active ester compound (A) essentially comprises at least one of the following (A1) to (A4).
Active ester compound (A1): esterified active ester compound (A2) of a compound (a1) having one phenolic hydroxyl group in the molecular structure and an aromatic polycarboxylic acid or its acid halide (a2): in the molecular structure An esterified active ester resin (A3) of a compound (a3) having two or more phenolic hydroxyl groups and an aromatic monocarboxylic acid or acid halide (a4) thereof: a compound having one phenolic hydroxyl group in the molecular structure (A1), an aromatic polycarboxylic acid or an acid halide thereof (a2) and an esterified active ester resin (A4) of a compound (a3) having two or more phenolic hydroxyl groups in the molecular structure: an aromatic polycarboxylic acid or Its acid halide (a2), compound (a3) having two or more phenolic hydroxyl groups in the molecular structure, and fragrance Monocarboxylic acids or esters of the acid halide (a4) The active ester composition according to claim 1, wherein 50% by mass or more of the acid anhydride (B) is the polyfunctional acid anhydride (B1). The polyfunctional acid anhydride (B1) has the following structural formulas (4-1) to (4-6).

(In the formula, each R ² is independently a hydrogen atom, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, an aralkyl group, or a halogen atom. R ⁴ is an aliphatic group having 1 to 6 carbon atoms. A hydrocarbon group, m is 0, 1 or 2, n is an integer of 2 to 4, and m + n is an integer of 2 to 4.)
The active ester composition according to claim 1, which is a compound represented by any one of: The active ester composition according to claim 1, comprising the acid anhydride (B) in a range of 0.1 to 500 parts by mass with respect to 100 parts by mass of the active ester compound (A). A curable composition comprising the active ester composition according to any one of claims 1 to 5 and a curing agent. A cured product of the curable composition according to claim 6. The semiconductor sealing material formed using the curable composition of Claim 6. A printed wiring board using the curable composition according to claim 6.