TWI751266B - Active ester composition - Google Patents

Abstract

The present invention provides an active ester composition having high curability and excellent dielectric properties, heat resistance, moisture absorption resistance, and other properties of a cured product, a cured product thereof, a semiconductor sealing material and a printed wiring board using the above-mentioned composition . The present invention relates to an active ester composition, a cured product thereof, a semiconductor sealing material and a printed wiring board using the above-mentioned composition, and the active ester composition contains an active ester compound (A) and an acid anhydride (B) as essential components, The said acid anhydride (B) has the polyfunctional acid anhydride (B1) which has two or more acid anhydride groups as an essential component.

Description

Active ester composition

The present invention relates to an active ester composition having high curability and excellent dielectric properties, heat resistance, moisture absorption resistance and other properties of the cured product, its cured product, a semiconductor sealing material and printed wiring using the above-mentioned composition substrate.

In the technical field of insulating materials used in semiconductors, multilayer printed circuit boards, etc., with the thinning and miniaturization of various electronic components, the development of new resin materials in accordance with these market trends is being pursued. The specific required properties are not only the heat resistance and moisture absorption resistance of the cured product, but also the low value of the dielectric constant and the dielectric loss tangent of the cured product as a measure to increase the speed and frequency of signals, and the It is also important that the physical properties such as glass transition temperature (Tg) and the like are not changed, and that the curing shrinkage and the coefficient of linear expansion are low as a measure against warpage or strain accompanying the reduction in thickness.

As a resin material excellent in heat resistance, dielectric properties, copper foil adhesion, etc. of the cured product, it is known to use di(α-naphthyl) isophthalate as epoxy resin Technology of resin hardener (refer to the following patent document 1). Regarding the epoxy resin composition described in Patent Document 1, when compared with the case of using a conventional epoxy resin hardener such as a phenol novolak type resin, by using di(α-naphthyl) Isophthalate is used as epoxy resin hardener, and the value of the dielectric constant or dielectric loss tangent of the hardened product is indeed low, but due to the low hardening property, it requires high temperature and long time hardening, so it is widely used in industry. At the time of utilization, there are problems in terms of reduction in productivity and energy consumption.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-82063

Therefore, the problem to be solved by the present invention is to provide an active ester composition having high curability and excellent dielectric properties, heat resistance, moisture absorption resistance and other properties of the cured product, the cured product thereof, and the composition obtained by using the above-mentioned composition. of semiconductor sealing materials and printed wiring boards.

The inventors of the present invention have made diligent studies in order to solve the above-mentioned problems. As a result, they have found that the following composition has high curability, and the cured product is excellent in various properties such as dielectric properties, heat resistance, and moisture absorption resistance, thereby completing the present invention; this composition Material system: It contains active ester compound and acid anhydride, and uses polyfunctional acid anhydride with two or more acid anhydride groups as acid anhydride.

That is, the present invention relates to an active ester composition comprising, as essential components, an active ester compound (A) and an acid anhydride (B), wherein the acid anhydride (B) is a polyfunctional acid anhydride (B1) having two or more acid anhydride groups. as an essential ingredient.

The present invention further relates to a curable composition comprising the above-mentioned active ester composition and a curing agent.

The present invention further relates to a cured product which is a cured product of the above-mentioned curable composition.

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

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

According to the present invention, there can be provided an active ester composition having high curability and excellent in dielectric properties, heat resistance, moisture absorption resistance and other properties of a cured product, a cured product thereof, a semiconductor sealing material using the above composition, and printed wiring board.

Hereinafter, the present invention will be described in detail.

The active ester composition of the present invention is characterized by comprising an active ester compound (A) and an acid anhydride (B) as essential components, and the acid anhydride (B) is an essential polyfunctional acid anhydride (B1) having two or more acid anhydride groups Element.

The specific structure of the active ester compound (A) is not particularly limited as long as it is a compound having an aromatic polyester structure in its molecular structure. In addition, the molecular weight is not particularly limited, and may be a compound with a single molecular weight, or an oligomer or polymer having a molecular weight distribution. Specific examples of the active ester compound (A) include the following (A1) to (A4). In addition, these are only examples of the active ester compound (A), and the active ester compound (A) of this invention is not limited to them. 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): ester compound of compound (a1) having one phenolic hydroxyl group in molecular structure and aromatic polycarboxylic acid or its acid halide (a2)

Active ester compound (A2): ester compound of a compound (a3) having two or more phenolic hydroxyl groups in its molecular structure and an aromatic monocarboxylic acid or its acid halide (a4)

Active ester resin (A3): compound (a1) having one phenolic hydroxyl group in its molecular structure, aromatic polycarboxylic acid or its acid halide (a2), and compound (a3) having two or more phenolic hydroxyl groups in its molecular structure ) esters

Active ester resin (A4): aromatic polycarboxylic acid or its acid halide (a2), compound (a3) having two or more phenolic hydroxyl groups in its molecular structure, and aromatic monocarboxylic acid or its acid halide (a4) ) esters

Specific examples of the compound (a1) having one phenolic hydroxyl group in the above-mentioned molecular structure include: phenol or phenol compounds having one or more substituents on the aromatic nucleus of phenol; naphthol or naphthol having one or more substituents on the aromatic nucleus Naphthol compounds with multiple substituents; anthracenol compounds with one or more substituents on the aromatic nucleus of anthracenol or anthracenol, etc. 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, an aralkyl group, and the like. The above-mentioned aliphatic hydrocarbon group may be any of a linear type and a branched type, and may have an unsaturated bond in the structure. Specifically, 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, a nonyl group, etc. are mentioned. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a structural moiety in which the above-mentioned aliphatic hydrocarbon group, an alkoxy group, a halogen atom, and the like are substituted on these aromatic nuclei. Examples of the aryloxy group include a phenoxy group, a naphthyloxy group, an anthraceneoxy group, and a structural moiety in which the above-mentioned alkyl group, an alkoxy group, a halogen atom, and the like are substituted on the aromatic nucleus thereof. Examples of the above-mentioned aralkyl group include phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl, and structural sites in which the above-mentioned alkyl group, alkoxy group, halogen atom, etc. are substituted on the aromatic nucleus of these, and the like. . The compound (a1) which has one phenolic hydroxyl group in the said molecular structure may be used individually by 1 type, and may use 2 or more types together.

Among them, a phenol compound or a naphthol compound is preferable, and a phenol compound or a naphthol compound or an aromatic nucleus of phenol, naphthol, or the like is more preferable in that a cured product excellent in various properties such as dielectric properties and heat resistance can be obtained. Compounds having one or two of the above substituents. The substituent on the aromatic nucleus is preferably an aliphatic hydrocarbon group or an aralkyl group having 1 to 6 carbon atoms.

The above-mentioned aromatic polycarboxylic acid or its acid halide (a2) includes, for example, benzenedicarboxylic acid such as isophthalic acid and terephthalic acid; and benzenetricarboxylic acid such as 1,2,4-benzenetricarboxylic acid; Naphthalene dicarboxylic acids such as naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid; acid halogenation of these compounds; compounds with one or more substituents on the aromatic nucleus, etc. As said acid halide, acid chloride, acid bromide, acid fluoride, acid iodide, etc. are mentioned. Moreover, as a substituent on an aromatic nucleus, an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, an aralkyl group, etc. are mentioned, and each specific example is as mentioned above. The said aromatic polycarboxylic acid or its acidic halide (a2) may be used individually, respectively, and may use 2 or more types together. Among them, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid or acid halides thereof are preferred in that a cured product excellent in various properties such as dielectric properties and heat resistance can be obtained.

Regarding the compound (a3) having two or more phenolic hydroxyl groups in the above molecular structure, for example, one or more kinds of various aromatic polyhydroxy compounds or the compound (a1) having one phenolic hydroxyl group in the above molecular structure can be used as a reaction Raw material novolak resin, one or more compounds (a1) having a phenolic hydroxyl group in the above molecular structure and any one of the following structural formulas (x-1) to (x-5) represented by The compound (x) is a reaction product and the like as an essential reaction raw material.

[In the formula, h is 0 or 1. R ^{1 is} each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and i is 0 or an integer of 1 to 4. Z is any one of vinyl, halomethyl, hydroxymethyl, and alkoxymethyl. 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 from 1 to 4. ]

As for the above-mentioned various aromatic polyhydroxy compounds, for example, in addition to dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydric onion, trihydric onion, tetrahydric onion, biphenol, In addition to tetrahydroxybiphenyl, bisphenol, and the like, compounds having one or more substituents on the aromatic nucleus thereof can also be cited. The substituents on the aromatic nucleus include aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, aralkyl groups, and the like, and specific examples of each are as described in the above paragraphs.

^{Regarding R 1} in the above structural formulas (x-1) to (x-5), specific examples of aliphatic hydrocarbon group, alkoxy group, halogen atom, aryl group, aryloxy group, and aralkyl group are as described in the above paragraphs . In addition, the reaction between the compound (a1) having a phenolic hydroxyl group in the molecular structure and the compound (x) can be carried out by the following method, that is, under the condition of an acid catalyst, at a temperature of about 80 to 180° C. Heating and stirring are carried out under temperature conditions.

The compound (a3) which has two or more phenolic hydroxyl groups in the said molecular structure may be used independently, respectively, and may use two or more types together. Among them, the above-mentioned aromatic dihydroxy compound is preferably dihydroxynaphthalene or a compound having a substituent on its aromatic nucleus, and more preferably an aromatic Alkyl dihydroxynaphthalene. As the novolak-type resin using one or more of the above-mentioned compounds (a1) as reaction raw materials, it is preferable to use phenol, naphthol, or the like, which has one or two aliphatic carbon atoms having 1 to 6 carbon atoms on its aromatic nucleus. A compound of a hydrocarbon group or an aralkyl group is used as the novolak type resin of the compound (a1). As the reaction product using the above-mentioned compound (a1) and the above-mentioned compound (x) as necessary reaction raw materials, it is preferable to use phenol, naphthol, or the like, which has one or two aliphatic carbon atoms having 1 to 6 carbon atoms on its aromatic nucleus. As the above-mentioned compound (a1), the compound represented by any one of (x-1) to (x-4) is used as the above-mentioned compound (x).

As the above-mentioned aromatic monocarboxylic acid or its acid halide (a4), for example, benzoic acid or halogenated benzyl group, the above-mentioned alkyl group, alkoxy group, halogen atom, aryl group, Compounds such as aryloxy, aralkyl, etc. These and the like may be used alone, respectively, or two or more of them may be used in combination.

The above-mentioned active ester compound (A) can be produced, for example, by mixing and stirring the respective reaction raw materials at a temperature of about 40 to 65° C. in the presence of an alkali catalyst. The reaction can also be carried out in an organic solvent as required. In addition, after completion of the reaction, the reaction product may be purified by washing with water, reprecipitation, or the like.

As said alkali catalyst, sodium hydroxide, potassium hydroxide, triethylamine, pyridine etc. are mentioned, for example. These may be used independently, respectively, and may use 2 or more types together. In addition, it can also be used as an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide with higher catalyst energy is preferred.

Examples of the above-mentioned organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbitol acetic acid. Acetate solvents such as esters; carbitol solvents such as cellulose and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methyl Pyrrolidone etc. These can be used individually, or can be made into 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 active ester compound (A) to be obtained, and the like, and the following are particularly preferable.

In the production of the above-mentioned active ester compound (A1), the reaction ratio of the above-mentioned compound (a1) having a phenolic hydroxyl group in the above-mentioned molecular structure and the above-mentioned aromatic polycarboxylic acid or its acid halide (a2) is obtained in high yield. In this respect, the target active ester compound (A1) is preferably 1 mole in the above molecular structure with respect to the total of the carboxyl groups or acid halide groups possessed by the above-mentioned aromatic polycarboxylic acid or its acid halide (a2). The compound (a1) having one phenolic hydroxyl group is in a molar ratio of 0.95 to 1.05.

In the production of the above-mentioned active ester compound (A2), the reaction ratio of the compound (a3) having two or more phenolic hydroxyl groups in the above-mentioned molecular structure and the above-mentioned esterified product of the aromatic monocarboxylic acid or its acid halide (a4), In terms of obtaining the target active ester compound (A2) in high yield, it is preferably 1 mol relative to the total of the phenolic hydroxyl groups contained in the compound (a3) having two or more phenolic hydroxyl groups in the above-mentioned molecular structure , the above-mentioned aromatic monocarboxylic acid or its acid halide (a4) is in a ratio of 0.95 to 1.05 moles.

In the production of the above-mentioned active ester resin (A3), the compound (a1) having one phenolic hydroxyl group in the above-mentioned molecular structure, the above-mentioned aromatic polycarboxylic acid or its acid halide (a2), and the above-mentioned molecular structure have two or more. The reaction ratio of the compound (a3) having a phenolic hydroxyl group is preferably the ratio of the molar number of the hydroxyl group possessed by the compound (a1) having one phenolic hydroxyl group in the above-mentioned molecular structure and the molar number of the hydroxyl group having two or more phenolic hydroxyl groups in the above-mentioned molecular structure. The ratio of the molar number of the hydroxyl group that the compound (a3) has is 10/90 to 75/25, more preferably 20/80 to 60/40. Moreover, it is preferable that the compound (a1) having one phenolic hydroxyl group in the above-mentioned molecular structure and the The total of the hydroxyl groups which the compound (a3) which has two or more phenolic hydroxyl groups in the said molecular structure has the range of 0.9-1.1 mol.

In the production of the above-mentioned active ester compound (A3), according to the reaction ratio of each raw material, a part of "the compound (a1) having one phenolic hydroxyl group in the molecular structure and the aromatic polycarboxylic acid or its acid halogenation can also be generated. "Ester compound of compound (a2)", namely active ester compound (A1). In this case, the content thereof is preferably 40% of the lesser 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 graph measured under the following conditions.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd., Column: Guard column "HXL-L" manufactured by Tosoh Co., Ltd.

+"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+"TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data processing: "GPC-8020 model II version 4.10" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40°C

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Standard: The following monodisperse polystyrene with known molecular weight is used according to the measurement manual of "GPC-8020 model II version 4.10" mentioned above.

(using polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: 1.0 mass % tetrahydrofuran solution in terms of resin solid content was filtered with a microfilter (50 μl)

In the production of the above-mentioned active ester compound (A4), the above-mentioned aromatic polycarboxylic acid or its acid halide (a2), the above-mentioned compound (a3) having two or more phenolic hydroxyl groups in the above-mentioned molecular structure, and the above-mentioned aromatic monocarboxylic acid The reaction ratio of its acid halide (a4) is preferably 1 mol relative to the total of the carboxyl groups or acid halide groups possessed by the above-mentioned aromatic monocarboxylic acid or its acid halide (a4) and the above-mentioned aromatic polycarboxylate. The ratio of the total of the carboxyl groups or acid halide groups which the acid or its acid halide (a2) has is in the range of 0.5 to 5 mol, more preferably in the range of 0.8 to 3 mol. In addition, it is preferable that the above-mentioned aromatic polycarboxylic acid or its acid halide (a2) and the above-mentioned aromatic monohydroxyl group are preferably used in 1 mole of hydroxyl groups of the compound (a3) having two or more phenolic hydroxyl groups in the above-mentioned molecular structure. The total of the carboxyl groups or acid halide groups which the carboxylic acid or its acid halide (a4) has is in the range of 0.9 to 1.1.

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

The above-mentioned active ester resins (A3) and (A4) preferably have a softening point measured based on JIS K7234 in the range of 80 to 200°C, more preferably in the range of 85 to 180°C. Moreover, the range of 150-350 g/equivalent is preferable from the viewpoint of excellent curability or the balance of each performance of hardened|cured material about the functional group equivalent weight. Furthermore, in the present invention, the functional group in the active ester resin refers to an ester bond site and a phenolic hydroxyl group in the active ester resin. In addition, the functional group equivalent of an active ester resin is a value calculated from the addition amount of a reaction raw material.

The specific structure of the acid anhydride (B) is not particularly limited as long as it is a compound having one or more acid anhydride groups in the molecular structure, and various compounds can be used. In addition, in this invention, an acid anhydride group means the structural part represented by 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 one of a monomolecular compound, an oligomer, and a polymer may be used. For the purpose of reducing the viscosity of the composition, it is preferable to use a monomolecular compound to improve the toughness of the cured product or For purposes such as flexibility, oligomers or polymers are preferred.

In this invention, the polyfunctional acid anhydride (B1) which has two or more acid anhydride groups is used as the said 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. Among them, it is preferable to use a monomolecular compound as the above-mentioned polyfunctional acid anhydride (B1) in that the viscosity of the composition can be reduced and the active ester composition having excellent physical properties of the cured product is obtained. It is especially preferable that the ratio of the monomolecular compound in the polyfunctional acid anhydride (B1) is 50 mass % or more, More preferably, it is 80 mass % or more.

Examples of the monomolecular compound in the polyfunctional acid anhydride (B1) include, for example, a compound represented by the following structural formula (4) in addition to pyromellitic dianhydride, hexanetetracarboxylic dianhydride, and the like. Moreover, as an example of the oligomer or polymer in the said polyfunctional acid anhydride (B1), the copolymer of styrene and maleic anhydride, etc. are mentioned.

V-W-V (4)

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

{In the formula, R ² is a bonding point with W, or is each independently any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and a halogen atom. The position of the acid anhydride group in structural formula (V-2) and structural formula (V-5) is not fixed, and it can also be an isomer}]

Specific examples of the R ^2, the above-described structural formulas include (x-1) ~ (x- 5) In the embodiment shown by R ¹ and the like.

W in the above-mentioned structural formula (4) is a direct bond or a divalent linking group, and the specific structure thereof is not particularly limited, and can be appropriately selected according to the desired properties of the cured product and the like. Examples of the divalent linking group include, for example, a structural moiety composed of a linear or branched alkylene group, a carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, an ester bond, and a combination thereof, etc. . As an example of a compound in which W is a structural site containing an ester bond, for example, one or more of the compounds represented by the following structural formulas (v-1) to (v-7) R ³ is a carboxyl group. It is obtained by reacting the compound with various polyol compounds or their alkyl esters in any ratio. The above-mentioned polyhydric alcohol compound includes, for example, aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, pentanediol, glycerin, trimethylolpropane, ditrimethylolpropane, neopentaerythritol, and dipeoerythritol. Alcohol compounds; aromatic polyol compounds such as biphenol, bisphenol, etc.; (poly)oxyethylene group ((poly)oxyethylene group) chains, (poly)oxypropylene group ((poly)oxypropylene group (poly)oxypropylene group (poly)oxypropylene group (poly)oxypropylene group (poly)oxypropylene group) chain, (poly)oxytetramethylene ((poly)oxytetramethylene group) chain and the like (poly)oxyalkylene modified body of (poly)oxyalkylene chain, etc.

{In the formula, R ^{3 is} each independently any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, a halogen atom, and a carboxyl group. The position of the acid anhydride group in structural formula (v-2) and structural formula (v-5) is not fixed, and it can also be an isomer}]

Even in the compound represented by the above-mentioned structural formula (4), it is preferable that V is the structural formula in terms of becoming an active ester composition excellent in various physical properties such as the dielectric properties, heat resistance, and moisture absorption resistance of the cured product. The one represented by any one of (V-1) to (V-4) is particularly preferably one represented by any one of the following structural formulae (4-1) to (4-6).

(in the formula, R ^{2 is} each independently any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and a halogen atom. R ⁴ is an aliphatic having 1 to 6 carbon atoms Hydrocarbon group. m is 0, 1 or 2, n is an integer of 2~4, m+n is an integer of 2~4)

In this invention, as the said acid anhydride (B), the monofunctional acid anhydride (B2) which has one acid anhydride and the said polyfunctional acid anhydride (B1) may be used together. As for the monofunctional acid anhydride (B2), for example, in the above-mentioned structural formulas (v-1) to (v-7), R ³ is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an aryl group. A compound of any one of an alkyl group and a halogen atom, and the like. In the case of using a monofunctional acid anhydride (B2) in combination, the ratio of the above-mentioned polyfunctional acid anhydride (B1) in the above-mentioned acid anhydride (B) is preferably 50 mass % or more in terms of fully exerting the effect achieved by the present invention, More preferably, it is 80 mass % or more, and particularly preferably 90 mass % or more.

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

Its acid anhydride (B) can be obtained in the form of a commercial product. Examples of commercially available products include the RIKACID series from Nippon Rika Co., Ltd., the EPICLON series from DIC Co., Ltd., and the like.

In the active ester composition of the present invention, the blending ratio of the active ester compound (A) and the acid anhydride (B) can be appropriately adjusted according to the desired curability or the physical properties of the cured product. In terms of being excellent in balance with the physical properties of the cured product, the acid anhydride (B) is preferably contained in a range of 0.1 to 500 parts by mass, more preferably 10 to 400 parts by mass, relative to 100 parts by mass of the active ester compound (A). The range of mass parts contains the said acid anhydride (B).

The curable composition of the present invention contains the above-mentioned active ester composition and a curing agent. As long as the above-mentioned curing agent is a compound capable of reacting with the active ester composition of the present invention, various compounds can be used without particular limitation. As an example of a hardening|curing agent, an epoxy resin is mentioned, for example. As said epoxy resin, the polyglycidyl ether etc. of the compound (a3) which has two or more phenolic hydroxyl groups in the said molecular structure are mentioned, for example.

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 properties of the cured product and the like. As an example of blending when an epoxy resin is used as a curing agent, it is preferable that the total of the functional groups in the active ester composition is 0.7 with respect to the total of 1 mol of epoxy groups in the epoxy resin. ~1.5 molar ratio. Furthermore, in the present invention, the functional group in the active ester composition refers to 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 amount of reaction raw materials added. In addition, 1 molar system of an acid anhydride group is calculated as a single function.

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

化合物；氰酸酯樹脂；雙馬來亞醯胺樹脂；苯乙烯-順丁烯二酸酐樹脂；以二烯丙基雙酚或異三聚氰酸三烯丙基酯為代表之含烯丙基樹脂；聚磷酸酯或磷酸酯-碳酸酯共聚物等。該等可分別單獨使用，亦可併用2種以上。 The curable composition of the present invention may further contain other resin components. As for other resin components, for example, phenolic hydroxyl group-containing compounds such as the compound (a3) having two or more phenolic hydroxyl groups in the above-mentioned molecular structure; diaminodiphenylmethane, diethylenetriamine, triethylenetriamine, Amine compounds such as ethylenetetramine, diaminodiphenylene, isophorone diamine, imidazole, BF ₃ -amine complexes, guanidine derivatives; dicyandiamine, dimerization of hypolinoleic acid amide compounds such as polyamide resins synthesized from ethylenediamine and ethylenediamine;

Compound; cyanate ester resin; bismaleimide resin; styrene-maleic anhydride resin; allyl group represented by diallyl bisphenol or triallyl isocyanurate Resin; polyphosphate or phosphate-carbonate copolymer, etc. These may be used independently, respectively, and may use 2 or more types together.

The blending ratio of these other resin components is not particularly limited, and can be appropriately adjusted according to the desired properties of the cured product. As an example of a blending ratio, it is preferable to use it in the range of 1-50 mass % in the curable composition of this invention.

The curable composition of the present invention may optionally contain various additives such as flame retardants, inorganic fillers, silane coupling agents, mold release agents, pigments, and emulsifiers.

化合物、三聚氰酸化合物、異三聚氰酸化合物、啡噻

等氮系阻燃劑； 聚矽氧油、聚矽氧橡膠、聚矽氧樹脂等聚矽氧系阻燃劑；金屬氫氧化物、金屬氧化物、金屬碳酸鹽化合物、金屬粉、硼化合物、低熔點玻璃等無機阻燃劑等。於使用該等阻燃劑之情形時，較佳為於硬化性組成物中為0.1~20質量%之範圍。 Examples of the flame retardant include red phosphorus, ammonium phosphates such as red phosphorus, ammonium dihydrogen phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and other inorganic phosphorus compounds; (phosphinic acid) compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10 -dihydro-9-oxa-10-phospha phenanthrene-10-oxide), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phospha phenanthrene-10-oxide, 10- Cyclic organophosphorus compounds such as (2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and compounds obtained by reacting them with epoxy resins or phenol resins Derivatives and other organophosphorus compounds; three

Compounds, Cyanuric Compounds, Isocyanuric Compounds, Phosphatidyl

and other nitrogen-based flame retardants; polysiloxane-based flame retardants such as polysiloxane oil, polysiloxane rubber, and polysiloxane resin; metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, Inorganic flame retardants such as low melting point glass, etc. When these flame retardants are used, it is preferable to be in the range of 0.1-20 mass % in a curable composition.

The above-mentioned inorganic filler is blended, for example, when the curable composition of the present invention is used for a semiconductor sealing material. Examples of the above-mentioned inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like. Among them, the above-mentioned fused silica is preferred in that it can incorporate more inorganic fillers. The above-mentioned fused silica can be used in either a crushed or spherical shape, but in order to increase the blending amount of the fused silica and suppress the rise of the melt viscosity of the curable composition, the spherical shape is preferably used. 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 blended in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

Furthermore, when the curable composition of the present invention is used in applications such as conductive pastes, conductive fillers such as silver powder or copper powder can be used.

The active ester composition of the present invention and the curable composition using the same are characterized by high curability, excellent dielectric properties, heat resistance, moisture absorption resistance and other physical properties of the cured product. In addition, it is one that is also sufficiently high in the usual required properties required for resin materials such as "solubility in general-purpose organic solvents or storage stability". Therefore, in addition to electronic material applications such as semiconductor sealing materials, printed wiring boards, and resist materials, it can be widely used in applications such as coatings, adhesives, and molded articles.

When the curable composition of the present invention is used for a semiconductor sealing material, it is generally preferable to blend an inorganic filler. The semiconductor sealing material can be prepared by mixing the blend using, for example, an extruder, a kneader, a roll, or the like. As a method of molding a semiconductor package using the obtained semiconductor sealing material, for example, the semiconductor sealing material is molded using a casting molding machine, a transfer molding machine, an injection molding machine, etc., and further heated at a temperature of 50 to 200° C. for 2 to 200 °C. The 10-hour method can obtain a semiconductor device as a molded product by this method.

When the curable composition of the present invention is used for a printed wiring board application or a build-up adhesive film application, it is generally preferable to mix and dilute an organic solvent for use. The above-mentioned organic solvents include: methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellulose, ethyl diethylene glycol ethyl acid ester, propylene glycol monomethyl ether acetate, etc. The type or blending amount of the organic solvent can be appropriately adjusted according to the use environment of the curable composition. For example, in the use of printed wiring boards, methyl ethyl ketone, acetone, dimethylformamide, etc. are preferably used, and the boiling point is 160°C. The following polar solvents are preferably used in a proportion of 40 to 80 mass % of the nonvolatile content. In the application of build-up adhesive film, it is preferable to use ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, carbitol Acetate solvents such as acetate; carbitol solvents such as cellulose and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N- Methyl pyrrolidone, etc.; Preferably, it is used in the ratio which becomes 30-60 mass % of non-volatile components.

Moreover, the method of manufacturing a printed wiring board using the curable composition of the present invention includes, for example, a method of impregnating and curing a reinforcing base material with the curable composition to obtain a prepreg, and heating it by stacking it on a copper foil crimp. Examples of the above-mentioned reinforcing base material include paper, glass cloth, glass nonwoven cloth, polyaramide paper, polyaramide cloth, glass mat, glass roving, and the like. The impregnation amount of the curable composition is not particularly limited, but it is usually preferably prepared so that the resin component in the prepreg is 20 to 60% by mass.

[Example]

Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. The descriptions of "parts" and "%" in the examples are the quality standards unless otherwise specified.

The GPC measurement conditions in this example are as follows.

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd., Column: Guard column "HXL-L" manufactured by Tosoh Co., Ltd.

+"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+"TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data processing: "GPC 8020 model II version 4.10" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40°C

developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the above-mentioned "GPC 8020 model II version 4.10" measurement manual, the following monodisperse polystyrene with known molecular weight is used.

(Polystyrene used)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: obtained by filtering a 1.0 mass % tetrahydrofuran solution in terms of resin solid content with a microfilter (50 μl)

Production Example 1 Production of Active Ester Resin (A3-1)

Add the addition reactant of dicyclopentadiene and phenol (hydroxyl equivalent 165g/equivalent, softening point 85°C) 165g, 1- 144 g of naphthol and 1315 g of toluene were dissolved while the inside of the system was replaced with nitrogen under reduced pressure. Next, 200 g of isophthalic chloride was added and dissolved in the system while being replaced with nitrogen under reduced pressure. While performing nitrogen flushing, the reaction system was controlled to be below 60° C., and 434 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 1 hour to allow the reaction to proceed. After completion of the reaction, the reaction mixture was left to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer, stirring for about 15 minutes, and mixing, the mixture was left to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 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)

234.3 g of p-tert-butylphenol, 52.8 g of toluene, 52.8 g of a 37% by mass aqueous solution of formalin, and 49% of sodium hydroxide were added to a flask equipped with a thermometer, dropping funnel, condenser tube, fractionation tube, and agitator. 4.8g. It heated to 75 degreeC, stirring, and it stirred at the same temperature for 1 hour, and made it react. After completion of the reaction, 7.1 g of sodium dihydrogen phosphate was added for neutralization, 363.2 g of toluene was added, and the mixture was washed three times with 121.1 g of water. This was dried under heating and reduced pressure conditions to obtain 234.8 parts by mass of an intermediate (1) containing unreacted p-tert-butylphenol and a phenol resin. The hydroxyl equivalent of the intermediate (1) was 155 g/equivalent.

141.4 g of isophthalic chloride and 1,000 g of toluene were added to a flask equipped with a thermometer, dropping funnel, condenser, fractionation tube, and agitator, and dissolved in the system while being replaced with nitrogen under reduced pressure. 217 g of the intermediate (1) obtained previously was added, and it was melt|dissolved, carrying out nitrogen substitution under reduced pressure in the system. 0.4 g of tetrabutylammonium bromide was dissolved, the inside of the reaction system was controlled to be below 60° C. while flushing with nitrogen gas, and 280 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 1 hour to allow the reaction to proceed. After completion of the reaction, the reaction mixture was left 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 left to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the water layer became 7, and then it was dried under heating and reduced pressure conditions 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. In addition, the content of isophthalic acid bis(p-tert-butylphenol) in the active ester resin (A3-2) calculated from the GPC diagram was 10.1%.

Production Example 3 Production of Active Ester Resin (A3-3)

565 g of phenol and 106 g of benzaldehyde were added to a flask equipped with a thermometer, a condenser, a fractionation tube, and a stirrer, and the mixture was stirred and dissolved while being replaced with nitrogen under reduced pressure in the system. Next, 5.7 g of p-toluenesulfonic acid was added, and it was made to react at 135 degreeC for 3 hours. After completion of the reaction, the 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 equivalent of the intermediate (2) was 150 g/equivalent.

To a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 225 g of the above-mentioned intermediate (2), 102 g of isophthalic chloride, 70 g of benzyl chloride, and 1000 g of toluene were added to each side. The inside of the flask was stirred and dissolved while being replaced with nitrogen under reduced pressure. 0.5 g of tetrabutylammonium bromide was added, and while nitrogen flushing was performed, the reaction system was controlled below 60° C., and 327 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for another 1 hour. After completion of the reaction, it was left to stand for liquid separation, and the aqueous layer was removed. 340 g of water was added to the remaining toluene phase, the mixture was stirred for about 15 minutes and mixed, and the mixture was left to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the water layer became 7, and thereafter, it was dried under heating and reduced pressure conditions to obtain 340 g of 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)

202.0 g of isophthalic chloride and 1,250 g of toluene were added to a flask equipped with a thermometer, dropping funnel, condenser tube, fractionation tube, and agitator, and dissolved in the system while being replaced with nitrogen under reduced pressure. Next, 288.0 g of 1-naphthol was added, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve it. 0.63 g of tetrabutylammonium bromide was added, and while nitrogen flushing was performed, the reaction system was controlled below 60° C., and 400 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 1 hour to allow the reaction to proceed. After completion of the reaction, the reaction mixture was left to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer, stirring for about 15 minutes, and mixing, the mixture was left to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and thereafter, it was dried under heating and reduced pressure to obtain an active ester compound (A1-1). The melt viscosity of the active ester compound (A1-1) was 0.6 dPa·s.

Production Example 5 Production of Active Ester Compound (A1-2)

202.0 g of isophthalic chloride and 1,400 g of toluene were added to a flask equipped with a thermometer, dropping funnel, condenser, fractionation tube, and agitator, and dissolved in the system while replacing with nitrogen under reduced pressure. Next, 340.0 g of o-phenylphenol was added and dissolved in the system while being replaced with nitrogen under reduced pressure. 0.70 g of tetrabutylammonium bromide was added, and while nitrogen flushing was performed, the reaction system was controlled below 60° C., and 400 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 1 hour to allow the reaction to proceed. After completion of the reaction, the reaction mixture was left to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer, stirring for about 15 minutes, and mixing, the mixture was left to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and thereafter, it was dried under heating and reduced pressure to obtain an active ester compound (A1-2). The melt viscosity of the active ester compound (A1-2) was 0.2 dPa·s.

Production Example 6 Production of polyfunctional acid anhydride (B1-1)

458 g of 3-methyl-4-cyclohexane-1.2-dicarboxylic anhydride (hereinafter abbreviated as PMMA) and 542 g of maleic anhydride were added to a flask equipped with a condenser tube, a fractionation tube, and a stirrer. Heat to 200°C and stir for 4 hours. While maintaining the temperature at 200°C, the pressure in the system was reduced to 10 mmHg, and the unreacted raw materials were recovered. To 215 g of the crude product remaining in the reaction vessel, 600 g of methyl isobutyl ketone was added, and the mixture was heated to 110° C. to melt, and then cooled to room temperature to precipitate crystals. The obtained crystal was air-dried at normal temperature to obtain 123 g of the target 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 Example and the comparative example of this case is as follows.

‧Polyfunctional acid anhydride (B1-2): "Benzophenone tetracarboxylic dianhydride [BTDA]" manufactured by Daicel Co., Ltd., 3,3',4,4'-benzophenone tetracarboxylic dianhydride

‧Monofunctional acid anhydride (B2-1): "RIKACID MH-700" manufactured by Nippon Chemical Co., Ltd., a 7/3 (mass ratio) mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride

‧Epoxy resin (1): "HP-7200H" manufactured by DIC Co., Ltd., dicyclopentadiene type epoxy resin, epoxy group equivalent is 275g/equivalent

‧Epoxy resin (2): "N-655-EXP-S" manufactured by DIC Co., Ltd., cresol-type epoxy resin, epoxy group equivalent: 202 g/equivalent

Examples 1 to 3 and Comparative Example 1

A curable composition was prepared according to the following points, and various evaluation tests were performed. The results are shown in Table 1.

Manufacture of curable composition (1)

The active ester resin and the acid anhydride were added to the flask in the ratios shown in the following Table 1, and the flask was heated and stirred to 170°C while blowing nitrogen gas. After cooling to 150°C, the epoxy resin and dimethylaminopyridine were further blended and mixed to obtain a curable composition (1). The addition amount of dimethylaminopyridine was made into 0.5 mass % with respect to the total mass of an active ester compound, an acid anhydride, and an epoxy resin.

Determination of glass transition temperature (Tg)

The curable composition (1) was put into a mold frame and molded at 150° C. for 10 minutes using a press. The molded product was taken out from the mold frame, and was further hardened at 175°C for 5 hours. The hardened molded product was cut out into a size of 5 mm×54 mm×2.4 mm, and this was used as a test piece.

Using a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometrics), the rectangular tension method was used to heat the sample from room temperature to 280° C. under the conditions of a frequency of 1 Hz and a heating temperature of 3° C./min. The temperature at which the change in elastic modulus becomes the largest (tan δ is the largest) was set as the glass transition temperature and evaluated.

Hardening evaluation

The glass transition temperature (Tg) measurement was performed again after cooling the test piece after the previous measurement of the glass transition temperature (Tg) to room temperature. The difference (ΔTg) between the first glass transition temperature (Tg) measurement value and the second glass transition temperature (Tg) measurement value (ΔTg) was calculated and evaluated by the following criteria. The larger the ΔTg value, the lower the hardenability, and it is considered that a large amount of functional groups that are not fully reacted during molding remain.

A: ΔTg is 5°C or lower.

B: △Tg exceeds 5°C

Determination of dielectric constant and dielectric loss tangent

A test piece was produced using the same apparatus and conditions as the previous glass transition temperature (Tg) measurement. For the test piece that was stored for 24 hours in a room at 23°C and 50% humidity after heating and vacuum drying, according to JIS-C-6481, an impedance material analyzer (HP 4291B) manufactured by Agilent Technology Co., Ltd. was used. The dielectric constant and dielectric loss tangent at 1 GHz were measured.

Manufacture of curable composition (2)

Active ester resin, acid anhydride, and epoxy resin were added to the flask at the ratios shown in Table 1 below. Methyl ethyl ketone was added so that it might become 40 weight% of the whole, and it stirred, blowing nitrogen gas. Dimethylaminopyridine is appropriately added so that the gel time becomes 5 to 7 minutes to obtain a curable composition (2).

Finger touch evaluation of prepreg

Using the curable composition (2), a prepreg was produced under the following conditions. Touch evaluation of the obtained prepregs was performed. If the prepreg has a sticky feeling or a sticky feeling, the workability during processing and the storage stability of the prepreg will decrease.

A: No stickiness or stickiness

B: There is stickiness or stickiness

(Prepreg production conditions)

Base material: Glass cloth "#2116" (210×280mm) manufactured by Nitto Textile Co., Ltd.

Drying conditions: dry at 160°C for 3 minutes

Evaluation of moisture absorption resistance

A laminate was produced under the following conditions using the curable composition (2). The moisture absorption test was performed by placing the laminate in an environment of 85° C. and 85% RH for 168 hours. After the moisture absorption test, the laminate was immersed for 10 seconds in a solder bath that melted, and it was evaluated as A when there was no change in appearance, and as B when generation of voids and the like were observed.

(Conditions for making laminates)

Base material: Glass cloth "#2116" (210×280mm) manufactured by Nitto Textile Co., Ltd.

Copper foil: "JTC foil" (18μm) manufactured by JX Nippon Mining & Metals Co., Ltd.

Layers: 6

Prepreg conditions: 160℃

Curing conditions: at 200 ℃, 40kg / cm ² for 1.5 hours

Plate thickness after forming: 0.8mm

Examples 4 to 6 and Comparative Example 2

A curable composition was prepared according to the following points, and various evaluation tests were performed. The results are shown in Table 2.

Manufacture of curable composition (3)

The active ester compound and the acid anhydride were added to the flask at the ratio shown in the following Table 2, and the flask was heated and stirred to 170°C while blowing nitrogen gas. After cooling to 150°C, other components were further blended and mixed to obtain a curable composition (3).

Touch Evaluation of Curable Compositions

The touch evaluation of the curable composition (3) was performed under normal temperature conditions.

A: No stickiness or stickiness

B: There is stickiness or stickiness

Determination of glass transition temperature (Tg)

The curable composition (3) was put into a mold frame and molded at 150°C for 10 minutes using a press. The molded product was taken out from the mold frame, and was further hardened at 175°C for 5 hours. The hardened molded product was cut out into a size of 5 mm×54 mm×2.4 mm, and this was used as a test piece.

Using a viscoelasticity measuring device (“solid viscoelasticity measuring device RSAII” manufactured by Rheometrics), the rectangular tension method was used to heat the sample from room temperature to 280° C. under the conditions of a frequency of 1 Hz and a heating temperature of 3° C./min. The temperature at which the change in elastic modulus becomes the largest (tan δ is the largest) was set as the glass transition temperature and evaluated.

Hardening evaluation

The glass transition temperature (Tg) measurement was performed again after cooling the test piece after the previous measurement of the glass transition temperature (Tg) to room temperature. The difference (ΔTg) between the first glass transition temperature (Tg) measurement value and the second glass transition temperature (Tg) measurement value (ΔTg) was calculated and evaluated by the following criteria. The larger the ΔTg value, the lower the hardenability, and it is considered that a large amount of functional groups that are not fully reacted during molding remain.

A: ΔTg is 5°C or lower.

B: △Tg exceeds 5°C

Manufacture of curable composition (4)

The active ester compound and the acid anhydride were added to the flask at the ratio shown in the following Table 2, and the flask was heated and stirred to 170°C while blowing nitrogen gas. After cooling to 150°C, the epoxy resin and dimethylaminopyridine were blended and mixed to obtain a curable composition (4).

Determination of dielectric constant and dielectric loss tangent

Using the curable composition (4), a test piece was produced by the same method as the evaluation of curability. For the test piece that was stored for 24 hours in a room at 23°C and 50% humidity after heating and vacuum drying, according to JIS-C-6481, an impedance material analyzer (HP 4291B) manufactured by Agilent Technology Co., Ltd. was used. The dielectric constant and dielectric loss tangent at 1 GHz were measured.

Claims (8)

An active ester composition comprising an active ester compound (A) and an acid anhydride (B) as essential components, the acid anhydride (B) having a polyfunctional acid anhydride (B1) having two or more acid anhydride groups as an essential component, and the above The polyfunctional acid anhydride (B1) is a compound represented by any one of the following structural formulae (4-1), (4-2) and (4-6);

(in the formula, R ^{2 is} independently any one of hydrogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, halogen atom; R ⁴ is an aliphatic having 1 to 6 carbon atoms Group hydrocarbon group; m is 0, 1 or 2, n is an integer of 2~4, m+n is an integer of 2~4). The active ester composition according to claim 1, wherein the active ester compound (A) must be any one or more of the following (A1) to (A4); Ester compound of compound (a1) of phenolic hydroxyl group and aromatic polycarboxylic acid or its acid halide (a2); active ester compound (A2): compound (a3) with two or more phenolic hydroxyl groups in molecular structure and aromatic Esterates of monocarboxylic acids or their acid halides (a4); active ester resins (A3): compounds (a1), aromatic polycarboxylic acids or their acid halides (a2) having one phenolic hydroxyl group in the molecular structure, and esters of compounds (a3) having two or more phenolic hydroxyl groups in the molecular structure; Active ester resin (A4): aromatic polycarboxylic acid or its acid halide (a2), compound (a3) having two or more phenolic hydroxyl groups in its molecular structure, and aromatic monocarboxylic acid or its acid halide (a4) ) esters. 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 active ester composition of Claim 1 which contains the said acid anhydride (B) in the range of 0.1-500 mass parts with respect to 100 mass parts of said active ester compounds (A). A curable composition comprising the active ester composition according to any one of Claims 1 to 4, and a curing agent. A hardened product, which is the hardened product of the hardening composition described in claim 5. A semiconductor sealing material using the curable composition of claim 5. A printed wiring board using the curable composition according to claim 5.