JP2022100697A - Ester compound, polyester resin, curable composition, cured product, prepreg, printed wiring board, build-up film, semiconductor encapsulant, and semiconductor device - Google Patents

Abstract

To provide an ester compound causing little increase in the dielectric loss tangent when a cured product thereof is subjected to a hot and humid condition, a polyester resin, a curable composition, a cured product, a prepreg, a printed wiring board, a build-up film, a semiconductor encapsulant, and a semiconductor device.SOLUTION: The invention provides an ester compound (A) represented by general formula (1) in the figure. [In general formula (1), each Ar1 is independently an optionally substituted aryl group; each Ar2 is independently an optionally substituted arylene group; and R1 is a C4-20 aliphatic hydrocarbon group.]SELECTED DRAWING: Figure 1

Description

The present invention relates to ester compounds, polyester resins, curable compositions, cured products, prepregs, printed wiring boards, build-up films, semiconductor encapsulants, and semiconductor devices.

In recent years, the miniaturization and high performance of electronic devices have been progressing, and along with this, the required performance of various materials used has been improved. For example, in a semiconductor package substrate, the speed and frequency of signals are increasing, and a material having a low electrical energy loss, that is, a material having a low dielectric loss tangent is required.

As such a material having a low dielectric loss tangent, for example, a technique of using an active ester compound as a curing agent for an epoxy resin is known (see Patent Document 1). The epoxy resin composition described in Patent Document 1 has a characteristic that the dielectric loss tangent in the cured product is lower than that of a general epoxy resin composition using a phenol resin as a curing agent. However, the hygroscopicity is not sufficient, and the dielectric loss tangent value increases significantly when exposed to moist heat conditions.

Japanese Unexamined Patent Publication No. 2004-155990

Therefore, an object to be solved by the present invention is to provide a resin material in which the increase in dielectric loss tangent is small when the cured product is exposed to moist heat conditions.

As a result of diligent studies to solve the above problems, the present inventors have found that the ester compound having a specific molecular structure and the polyester resin containing the ester compound have a small increase in dielectric tangent when the cured product is exposed to moist heat conditions. This has led to the completion of the present invention.

That is, the present invention relates to the ester compound (A) represented by the following general formula (1).

［上記一般式（１）中のＡｒ^１はそれぞれ独立して置換基を有していてもよいアリール基である。Ａｒ^２はそれぞれ独立して置換基を有していてもよいアリーレン基である。Ｒ^１は炭素原子数４～２０の脂肪族炭化水素基である。］

[Ar ¹ in the above general formula (1) is an aryl group which may have an independent substituent. Ar ² is an arylene group which may have a substituent independently of each other. R ¹ is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. ]

The present invention further relates to a polyester resin containing the ester compound (A).

The present invention further relates to a curable composition containing the ester compound (A) or the polyester resin.

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

The present invention further relates to a prepreg using the curable composition.

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

The present invention further relates to a build-up film using the curable composition.

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

The present invention further relates to a semiconductor device using a semiconductor encapsulant using the curable composition.

According to the present invention, an ester compound, a polyester resin, a curable composition, a cured product, a prepreg, a printed wiring board, a build-up film, and a semiconductor seal, which have a small increase in dielectric adjacency when the cured product is exposed to moist heat conditions. Stopping materials and semiconductor devices can be provided.

FIG. 1 is a GPC chart of the polyester resin (1) obtained in Example 1. FIG. 2 is a GPC chart of the polyester resin (2) obtained in Example 2. FIG. 3 is a GPC chart of the polyester resin (3) obtained in Example 3.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
The ester compound (A) of the present invention is characterized by being represented by the following general formula (1).

［上記一般式（１）中のＡｒ^１は、置換基を有していてもよいアリール基である。Ａｒ^２は置換基を有していてもよいアリーレン基である。Ｒ^１は炭素原子数４～２０の脂肪族炭化水素基である。］

[Ar ¹ in the above general formula (1) is an aryl group which may have a substituent. Ar ² is an arylene group which may have a substituent. R ¹ is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. ]

Ar ¹ in the general formula (1) is an aryl group which may have a substituent. As a specific example thereof, for example, it has one or more substituents such as a phenyl group, a naphthyl group, and a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, and an alkynyloxy group on these aromatic rings. Structural parts and the like can be mentioned.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. The aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Specifically, an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group, a vinyl group, an allyl group and 1-butenyl. An alkenyl group having 2 to 4 carbon atoms such as a group, a 2-butenyl group and a 3-butenyl group, an ethynyl group, a propagyl group, a 1-butynyl group, a 2-butynyl group and a 3-butenyl group having 2 to 4 carbon atoms. Examples thereof include the alkylnyl group of 4. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group and the like. Examples of the alkenyloxy group include an alkenyloxy group having 2 to 4 carbon atoms such as a vinyloxy group, an allyloxy group, a 1-butenyloxy group, a 2-butenyloxy group and a 3-butenyloxy group. Examples of the alkynyloxy group include an alkynyloxy group having 2 to 4 carbon atoms such as an ethynyloxy group, a propagyloxy group, a 1-butynyloxy group, a 2-butynyloxy group and a 3-butynyloxy group.

Above all, since the curing reaction can be carried out by the ester compound (A) alone or in combination with another polymerizable unsaturated group-containing compound such as a maleimide resin, the Ar ¹ has at least the number of carbon atoms. It has 1 to 3 alkenyl groups of 2 to 4, the alkynyl group having 2 to 4 carbon atoms, the alkenyloxy group having 2 to 4 carbon atoms, and the alkynyloxy group having 2 to 4 carbon atoms. Is preferable. At this time, the Ar ¹ may have a substituent other than these.

Ar ² in the general formula (1) is an arylene group which may have a substituent. Specific examples thereof include a phenylene group, a naphthylene group, and one or a plurality of substituents such as a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, and an alkynyloxy group on the aromatic ring thereof. Structural parts and the like can be mentioned. Specific examples of the halogen atom, the aliphatic hydrocarbon group, the alkoxy group, the alkenyloxy group, and the alkynyloxy group include the same as those mentioned as examples of the substituent on Ar ¹ .

Among them, Ar ² is preferably a structural moiety having one or more of a halogen atom, an aliphatic hydrocarbon group, and an alkoxy group on a phenylene group, a naphthylene group, and an aromatic ring thereof, and is preferably a phenylene group. Alternatively, a naphthylene group is preferable.

R ¹ in the general formula (1) is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. The aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Above all, since the effect of excellent dielectric properties in the cured product becomes more remarkable, R ¹ is preferably a linear alkylene group, and the number of carbon atoms thereof is preferably in the range of 6 to 14.

The method for producing the ester compound (A) is not particularly limited, but as an example, for example, the phenolic hydroxyl group-containing compound (a1) represented by the following structural formula (3) and the following general formula (4) are represented. Examples thereof include a method using an aromatic dicarboxylic acid or an acid halide (a2) thereof, and a diol compound (a3) represented by the following structural formula (5) as a reaction raw material.

［上記一般式（３）中のＡｒ^１は置換基を有していてもよいアリール基である。一般式（4）中のＡｒ^２は置換基を有していてもよいアリーレン基である。一般式（５）中のＲ^１は炭素原子数４～２０の脂肪族炭化水素基である。］

[Ar ¹ in the above general formula (3) is an aryl group which may have a substituent. Ar ² in the general formula (4) is an arylene group which may have a substituent. R ¹ in the general formula (5) is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. ]

Specific examples and preferred ones of Ar ¹ , Ar ² , and R ¹ in the general formulas (3) to (5) are the same as those in the general formula (1).

When the ester compound (A) is produced from the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its acid halide (a2), and the diol compound (a3), the ester is contained in the reaction product. By-products other than compound (A) may occur. In the present invention, the ester compound (A) may be isolated and purified from the reaction product and used, or the reaction product may be used as the polyester resin of the present invention.

When the reaction product of the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its acid halide (a2), and the diol compound (a3) is used as it is in the polyester resin of the present invention, the phenolic hydroxyl group is used. In addition to the contained compound (a1), the aromatic dicarboxylic acid or its acid halide (a2), and the diol compound (a3), reaction raw materials other than these may be used in combination. In that case, since the polyester resin is superior in dielectric properties in the cured product, the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or the acid halide thereof (a2) occupying 100 parts by mass of the reaction raw material of the polyester resin. The total mass of the diol compound (a3) is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and particularly preferably 95 parts by mass or more.

The reaction method of the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its acid halide (a2), and the diol compound (a3) is not particularly limited, and for example, a method of collectively reacting reaction raw materials. It may be produced by a multi-stage reaction in which a part of the reaction raw material is reacted first and the remaining reaction raw material is reacted later. In particular, since the ester compound (A) can be produced more efficiently, an intermediate (M) which is an esterified product of the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or an acid halide thereof (a2). ) Is produced in advance, and the method of reacting this with the diol compound (a3) is preferable.

The reaction between the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) is, for example, a method of heating and stirring under a temperature condition of about 20 to 70 ° C. in the presence of an alkaline catalyst. Can be done by. The reaction may be carried out in an organic solvent if necessary. After completion of the reaction, the reaction product may be purified by washing with water, reprecipitation or the like, if desired.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diazabicycloundecene, diazabicyclononene 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 3 to 30% by mass. Of these, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable. The amount of the alkaline catalyst added is preferably in the range of 0.1 to 3 mol with respect to 1 mol of the hydroxyl group in the reaction raw material. Further, in order to increase the reaction efficiency, a phase transfer catalyst such as an alkylammonium salt or a crown ether may be used. These may be used alone or in combination of two or more. The amount of the phase transfer catalyst added is preferably in the range of 0.01 to 1% by mass with respect to the total mass of the reaction raw materials.

The organic solvent may be, for example, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, an acetate solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate or carbitol acetate, or carbitol such as cellosolve or butyl carbitol. Examples thereof include a solvent, an aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Each of these may be used alone or as a mixed solvent of two or more kinds. The amount of these organic solvents used is preferably in the range of 20 to 300% by mass with respect to the total mass of the reaction raw materials.

The reaction ratio between the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or the acid halide (a2) thereof is such that the ester compound (A) can be obtained in a higher yield, and thus the aromatic dicarboxylic acid. The amount of the phenolic hydroxyl group-containing compound (a1) is preferably in the range of 0.8 to 3 mol, and preferably in the range of 1.5 to 2.2 mol with respect to 1 mol of the acid or the acid halide (a2) thereof. Is more preferable.

The reaction between the intermediate (M), which is an esterified product of the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or the acid halide thereof (a2), and the diol compound (a3) is, for example, an alkali catalyst. It can be carried out by a method of heating and stirring under a temperature condition of about 50 to 250 ° C. in the presence of the above. The reaction may be carried out in an organic solvent if necessary. After completion of the reaction, it is preferable to distill off the phenolic hydroxyl group-containing compound (a1) produced as a result of the transesterification reaction. If desired, the reaction product may be purified by washing with water, reprecipitation, or the like.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diazabicycloundecene, diazabicyclononene 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%. Of these, diazabicycloundecene and diazabicyclononene having high catalytic ability are preferable. The amount of the alkaline catalyst added is preferably in the range of 0.01 to 10% by mass with respect to the total mass of the reaction raw materials. Further, in order to increase the reaction efficiency, a phase transfer catalyst such as an alkylammonium salt or a crown ether may be used.

The organic solvent may be, for example, a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone, an acetate solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate or carbitol acetate, or carbitol such as cellosolve or butyl carbitol. Examples thereof include a solvent, an aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Each of these may be used alone or as a mixed solvent of two or more kinds.

Since the reaction ratio between the intermediate (M) and the diol compound (a3) is such that the ester compound (A) can be obtained in a higher yield, the intermediate (M) is compared with the diol compound (a3). ) Is preferably used in excess. Specifically, it is preferable to use 1.1 to 5 mol of the intermediate (M), more preferably 1.5 to 4 mol, and 1.8 to 1 mol of the intermediate (M) with respect to 1 mol of the diol compound (a3). It is more preferable to use 3 mol.

The content of the ester compound (A) in the polyester resin of the present invention is calculated from the area ratio of the gel permeation chromatography (GPC) chart because the effect of excellent dielectric properties in the cured product becomes more remarkable. The value is preferably 10% or more, and preferably 15% or more. The upper limit thereof is preferably 60% or less, more preferably 45% or less. In addition, gel permeation chromatography (GPC) was measured under the measurement conditions described in the examples.

［上記一般式（２）中のＡｒ^１はそれぞれ独立して置換基を有していてもよいアリール基である。Ａｒ^２は置換基を有していてもよいアリーレン基である。］ Further, the polyester resin of the present invention preferably contains the ester compound (B) represented by the following general formula (2) because the effect of excellent dielectric properties in the cured product becomes more remarkable. The content of the ester compound (B) in the polyester resin is preferably 10% or more, preferably 15% or more, as a value calculated from the area ratio of the gel permeation chromatography (GPC) chart. More preferred. The upper limit thereof is preferably 50% or less, and more preferably 35% or less. In addition, gel permeation chromatography (GPC) was measured under the measurement conditions described in the examples.

[Ar ¹ in the above general formula (2) is an aryl group which may have an independent substituent. Ar ² is an arylene group which may have a substituent. ]

Specific examples and preferred ones of Ar ¹ and Ar ² in the general formula (2) are the same as those in the general formula (1).

The polyester resin of the present invention may contain the ester compound (C) represented by the following general formula (6) in addition to the ester compound (A) and the ester compound (B).

［上記一般式（１）中のＡｒ^１はそれぞれ独立して置換基を有していてもよいアリール基である。Ａｒ^２はそれぞれ独立して置換基を有していてもよいアリーレン基である。Ｒ^１は炭素原子数４～２０の脂肪族炭化水素基である。ｎは２以上の整数である。］

[Ar ¹ in the above general formula (1) is an aryl group which may have an independent substituent. Ar ² is an arylene group which may have a substituent independently of each other. R ¹ is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. n is an integer of 2 or more. ]

Specific examples and preferred ones of Ar ¹ , Ar ² , and R ¹ in the general formula (6) are the same as those in the general formula (1). In the general formula (6), n is an integer of 2 or more, and more preferably an integer of 2 to 10.

The number average molecular weight (Mn) of the polyester resin of the present invention is preferably in the range of 500 to 5,000, more preferably in the range of 600 to 3,000. The weight average molecular weight (Mw) is preferably in the range of 700 to 7,000, more preferably in the range of 800 to 5,000. In the present specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polyester resin are measured by gel permeation chromatography (GPC) under the measurement conditions described in Examples.

When the ester compound (A) of the present invention has a polymerizable unsaturated group such as an alkenyl group, an alkynyl group, an alkenyloxy group, or an alkynyloxy group as a substituent on Ar ¹ or Ar ² in the general formula (1). Alternatively, it can be used as a curable composition by the polyester resin containing it alone or by blending it with another polymerizable unsaturated group-containing compound such as a maleimide compound. In this case, the curing reaction generally proceeds by light irradiation or heating. The heating temperature and heating time at the time of heat curing are appropriately adjusted depending on the compounding components in the curable composition and the like, but are preferably about 1 to 24 hours at 100 to 300 ° C.

Examples of the maleimide compound include those represented by any of the following general formulas (6) to (9). Examples of commercially available maleimide resins include "BMI-1000", "BMI-2000", "BMI-2300", "BMI-3000", "BMI-4000", and "BMI" manufactured by Daiwa Kasei Kogyo Co., Ltd. -6000 "," BMI-7000 "," BMI-8000 "," BMI-TMH ", etc.," BMI "," BMI-70 "," BMI-80 ", etc. manufactured by KAI Kasei Co., Ltd., Tokyo Kasei Kogyo Examples thereof include "B1109", "N1971", "B4807", "P0778", and "P0976" manufactured by Co., Ltd. The maleimide compound may be used alone or in combination of two or more.

［上記一般式（６）中のＲ^２は二価の有機基である。上記一般式（７）～（９）中のＲ^３は炭素原子数１～８のアルキル基、ハロゲン原子、炭素原子数１～４のアルコキシ基、アリール基、アラルキル基のいずれかであり、ｎは０～３の整数である。上記一般式（７）のＸは炭素原子数１～６のアルキレン基、炭素原子数６～２０のシクロアルキレン基、アリーレン基、アルキレンアリーレンアルキレン基、酸素原子、硫黄原子、カルボニル基のいずれかであり、ｍは１以上の整数である。上記一般式（８）中のＲ^４は水素原子、炭素原子数１～４のアルキル基、アリール基のいずれかである。前記一般式（９）中のｌは３～６の整数である。］

[R ² in the above general formula (6) is a divalent organic group. R ³ in the above general formulas (7) to (9) is any one of an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an aryl group, and an aralkyl group, and n Is an integer from 0 to 3. X in the above general formula (7) is any one of an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group, an alkylene arylene alkylene group, an oxygen atom, a sulfur atom, and a carbonyl group. Yes, m is an integer of 1 or more. R ⁴ in the above general formula (8) is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group. In the general formula (9), l is an integer of 3 to 6. ]

Regarding R ² in the general formula (6), specific examples of the divalent organic group include, for example, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group, and oxygen. Examples thereof include an atom, a sulfur atom, a carbonyl group, and a structural site in which two or more of these groups are linked. Specific examples of the compound represented by the general formula (6) include, for example, N, N'-ethylenebismaleimide, N, N'-hexamethylenebismaleimide, N, N'-(1,3-phenylene). Bismaleimide, N, N'-[1,3- (2-methylphenylene)] Bismaleimide, N, N'-[1,3- (4-methylphenylene)] Bismaleimide, N, N'-(1) , 4-Phenylene) bismaleimide, bis (4-maleimidephenyl) methane, bis (3-methyl-4-maleimidephenyl) methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanebismaleimide, Bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, bis (4-maleimidephenyl) sulfide, bis (4-maleimidephenyl) ketone, bis (4-maleimidecyclohexyl) methane, 1,4-bis (4-Maleimidephenyl) cyclohexane, 1,4-bis (maleimidemethyl) cyclohexane, 1,4-bis (maleimidemethyl) benzene, 1,3-bis (4-maleimidephenoxy) benzene, 1,3-bis (3) -Maleimide phenoxy) benzene, bis [4- (3-maleimide phenoxy) phenyl] methane, bis [4- (4-maleimide phenoxy) phenyl] methane, 1,1-bis [4- (3-maleimide phenoxy) phenyl] Etan, 1,1-bis [4- (4-maleimidephenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidephenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimide) Phenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidephenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, 2,2-bis [4- (3-Maleimidephenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] butane, 2,2-bis [[4- (3-maleimidephenoxy) phenyl] -1,1, 1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidephenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-Maleimide phenoxy) biphenyl, 4,4-bis (4-maleimide phenoxy) biphenyl, bis [4- (3-maleimide phenoxy) phenyl] ketone, bis [4- (4-maleimide phenoki) Benzene] Benzene, 2,2'-bis (4-maleimidephenyl) disulfide, bis (4-maleimidephenyl) disulfide, bis [4- (3-maleimidephenoxy) phenyl] sulfide, bis [4- (4- (4-) Maleimide phenoxy) phenyl] sulfide, bis [4- (3-maleimide phenoxy) phenyl] sulfoxide, bis [4- (4-maleimide phenoxy) phenyl] sulfoxide, bis [4- (3-maleimide phenoxy) phenyl] sulfone, bis [4- (4-maleimide phenoxy) phenyl] sulfone, bis [4- (3-maleimide phenoxy) phenyl] ether, bis [4- (4-maleimide phenoxy) phenyl] ether, 1,4-bis [4- (4) 4-Maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3- (3-) Maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimide phenoxy) ) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidephenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4 -Bis [4- (3-maleimide phenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimide phenoxy) -3,5-dimethyl-α, α-Dimethylbenzyl] benzene, 4-methyl-1,3-phenylene bismaleimide, polyphenylmethanemaleimide and the like can be mentioned.

When the ester compound (A) of the present invention or the polyester resin containing the same has a polymerizable unsaturated group, the ester compound (A) or the ester compound (A) with respect to the total mass of the compound having a polymerizable unsaturated group in the curable composition. The proportion of the polyester resin containing this is not particularly limited, and is appropriately adjusted according to the desired resin performance, application, and the like. Above all, the ratio of the ester compound (A) or the polyester resin containing the ester compound (A) to 100 parts by mass of the total mass of the compound having a polymerizable unsaturated group in the curable composition is preferably 20% by mass or more, 25. It is more preferably in the range of about 75% by mass, and particularly preferably in the range of 30 to 60% by mass.

Since the ester compound (A) of the present invention and the polyester resin containing the ester compound (A) have an ester bond between aromatic rings in the structure, they function as a so-called active ester compound or resin. , Can be used as a curable composition. In this case, the curing reaction generally proceeds by heating. The heating temperature and the heating time are appropriately adjusted depending on the compounding components in the curable composition and the like, but are preferably about 1 to 24 hours at 100 to 300 ° C. Further, the curable composition of the present invention may contain both a polymerizable unsaturated group-containing compound such as the maleimide compound and an epoxy resin.

The epoxy resin is not particularly limited, but is not particularly limited. Novorak type epoxy resin such as resin; Aralkill type epoxy resin such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin; bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin , Bisphenol B type epoxy resin, Bisphenol BP type epoxy resin, Bisphenol C type epoxy resin, Bisphenol E type epoxy resin, Bisphenol F type epoxy resin, Bisphenol S type epoxy resin, Tetrabromo Bisphenol A type epoxy resin, etc. Biphenyl type epoxy resin such as biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, biphenyl skeleton and epoxy resin having diglycidyl oxybenzene skeleton; naphthalene type epoxy resin; binaphthol type epoxy resin; binaphthyl type epoxy resin; dicyclopentadiene Dicyclopentadiene type epoxy resin such as phenol type epoxy resin; glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenylsulfone; 2 , 6-Naphthalenedicarboxylic acid diglycidyl ester type epoxy resin, diglycidyl ester type epoxy resin such as glycidyl ester type epoxy resin of hexahydrohydroan phthalic acid; benzopyran such as dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyldibenzopyran Examples include type epoxy resins. These may be used alone or in combination of two or more.

When the curable composition of the present invention contains the epoxy resin, a curing agent for an epoxy resin other than the ester compound (A) of the present invention or the polyester resin may be used in combination. Examples of the curing agent for epoxy resin include active ester resins other than the ester compound (A) or polyester resin of the present invention, amine compounds, amide compounds, acid anhydrides, phenolic resins, cyanate ester resins, and benzoxazine resins. And so on.

When the curable composition of the present invention contains the epoxy resin, the blending ratio with the ester compound (A) of the present invention or the polyester resin and other curing agents for epoxy resins is the epoxy group in the curable composition. It is preferable that the total amount of the functional groups in the curing agent is 0.7 to 1.5 mol with respect to the total of 1 mol.

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

The curing accelerator is not particularly limited, and examples thereof include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, peroxides, and azo compounds. Can be mentioned.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphine and triethylphosphine; ethyltriphenyl. Phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-trilborate, triphenylphosphine triphenylboran, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium disianamide, Examples thereof include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

Amine-based curing accelerators include triethylamine, tributylamine, N, N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4]. .0] -Undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] -Nonen-5 (DBN) and the like.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 2-phenyl-. 4-Methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct, 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2- Examples thereof include methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5. , 7-Triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene, 1-methylbiguanide, Examples thereof include 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and the like.

Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenylurea, and 3- (4-chlorophenyl) -1,1. -Dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like can be mentioned.

Examples of the peroxide include dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dit-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexylperoxycarbonate, and azobisisobutyro. Examples include nitrile.

Among the above-mentioned curing accelerators, it is preferable to use dicumyl peroxide, 2-ethyl-4-methylimidazole, and dimethylaminopyridine.

The above-mentioned curing accelerator may be used alone or in combination of two or more.

The amount of the curing accelerator used is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 with respect to 100 parts by mass of the resin solid content of the curable composition. When the amount of the curing accelerator used is 0.01 parts by mass or more, it is preferable because the curing property is excellent. On the other hand, when the amount of the curing accelerator used is 5 parts by mass or less, it is preferable because the moldability is excellent.

The flame retardant may be, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphoric acid ester compounds, phosphonic acid. Compounds, phosphinic acid compounds, phosphin oxide compounds, phosphoran compounds, organonitrous-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) -10H-9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, etc. Cyclic organic phosphorus Organophosphorus compounds such as compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers and silicones. Silicone-based flame retardants such as resins; examples thereof include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and inorganic flame retardants such as low melting point glass. When these flame retardants are used, it is preferably in the range of 0.1 to 20% by mass in the curable resin composition.

The inorganic filler is blended, for example, when the curable resin composition of the present invention is used for semiconductor encapsulation material applications. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like. Above all, the molten silica is preferable because it is possible to blend a larger amount of the inorganic filler. The fused silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the curable composition, a spherical one is mainly used. Is preferable. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of 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 resin composition.

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

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 it with 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 amount of the organic solvent can be appropriately adjusted according to the usage environment of the curable composition. For example, in the case of printed wiring board applications, polar solvents such as methyl ethyl ketone, acetone, dimethylformamide, and cyclohexanone having a boiling point of 160 ° C or less are used. It is preferably present, and it is preferable to use it in a proportion such that the non-volatile content is 25 to 80% by mass. For build-up adhesive film applications, 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 carbitol such as cellosolve and butyl carbitol. 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 the non-volatile content at a ratio of 25 to 60% by mass.

Further, in the method of manufacturing a printed wiring board using the curable composition of the present invention, for example, the curable composition is impregnated into a reinforcing base material and cured to obtain a prepreg, which is then heated by superimposing the copper foil. A method of crimping can be mentioned. Examples of the reinforcing base material include paper, glass cloth, glass non-woven 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 adjust the resin content in the prepreg to be 20 to 60% by mass.

When the curable composition of the present invention is used as a semiconductor encapsulating material, it is generally preferable to add an inorganic filler. The semiconductor encapsulation material can be prepared by mixing the formulations using, for example, an extruder, a kneader, a roll, or the like. As a method of molding a semiconductor package using the obtained semiconductor encapsulating material, for example, the semiconductor encapsulating material is molded by casting or using a transfer molding machine, an injection molding machine, or the like, and further, the temperature is 50 to 200 ° C. A method of heating under the conditions for 2 to 10 hours can be mentioned, and a semiconductor device which is a molded product can be obtained by such a method.

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

<Measurement conditions for gel permeation chromatography (GPC)>
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene with known molecular weight was used in accordance with the measurement manual of "GPC-8320".
(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: Tetrahydrofuran solution of 1.0% by mass in terms of resin solid content filtered with a microfilter (50 μl)

< ¹³ C-NMR measurement conditions>
Equipment: "JNM-ECA500" manufactured by JEOL Ltd.
Measurement mode: Decoupling with reverse gate Solvent: Deuterated dimethyl sulfoxide Pulse angle: 30 ° pulse Sample concentration: 30% by mass
Number of integrations: 4,000 times Criteria for chemical shift: Peak of dimethyl sulfoxide: 39.5 ppm

<Measurement of FD-MS>
FD-MS was measured using a double-focusing mass spectrometer "AX505H (FD505H)" manufactured by JEOL Ltd.

(Example 1: Production of polyester resin (1))
101.0 g of isophthalic acid chloride and 397.0 g of toluene were charged in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve the flask. Then, 134.0 g of 2-allylphenol was charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve it. Further, 0.30 g of tetrabutylammonium bromide was added and dissolved. While performing a nitrogen gas purge, the temperature inside the system was controlled to 60 ° C. or lower, and 206.0 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Stirring was continued for 1.0 hour under the same temperature conditions. After completion of the reaction, the solution was allowed to stand and separated, and the aqueous layer was removed. Water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the solution was allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, water and toluene were removed by decanter dehydration to obtain a liquid intermediate (1). The ¹³ C-NMR chart of the intermediate (1) is shown in FIG. 1, the FD-MS chart is shown in FIG. 2, and the GPC chart is shown in FIG.

In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer, 60.0 g of 1,9-nonanediol, 298.4 g of the intermediate (1), diazabicycloundecene (DBU) 1. I charged 79g. After substituting nitrogen under reduced pressure in the system, the temperature was raised to 190 ° C., and the mixture was stirred at the same temperature for 3 hours. Then, 2-allylphenol was removed by vacuum distillation to obtain a polyester resin (1). The weight average molecular weight (Mw) of the polyester resin (1) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 1,848. Further, the content of the ester compound (A) in the polyester resin (1) calculated from the area ratio of the gel permeation chromatography (GPC) chart is 29%, and the content of the ester compound (B) is 21%. Met. The GPC chart of the polyester resin (1) is shown in FIG.

(Example 2: Production of polyester resin (2))
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer, 40.0 g of 1,6-hexanediol, 249.5 g of the intermediate (1), and diazabicycloundecene (DBU) 1. I charged 45g. After substituting nitrogen under reduced pressure in the system, the temperature was raised to 190 ° C., and the mixture was stirred at the same temperature for 3.5 hours. Then, 2-allylphenol was removed by vacuum distillation to obtain a polyester resin (2). The weight average molecular weight (Mw) of the polyester resin (2) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 1,489. Further, the content of the ester compound (A) in the polyester resin (2) calculated from the area ratio of the gel permeation chromatography (GPC) chart is 28%, and the content of the ester compound (B) is 21%. Met. The GPC chart of the polyester resin (2) is shown in FIG.

(Example 3: Production of polyester resin (3))
In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer, 50.0 g of 1,12-dodecanediol, 208.74 g of the intermediate (1), and diazabicycloundecene (DBU) 1. I charged 29g. After substituting nitrogen under reduced pressure in the system, the temperature was raised to 190 ° C., and the mixture was stirred at the same temperature for 7 hours. Then, 2-allylphenol was removed by vacuum distillation to obtain a polyester resin (2). The weight average molecular weight (Mw) of the polyester resin (3) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 1,647. Further, the content of the ester compound (A) in the polyester resin (3) calculated from the area ratio of the gel permeation chromatography (GPC) chart is 32%, and the content of the ester compound (B) is 26%. Met. The GPC chart of the polyester resin (3) is shown in FIG.

(Examples 4 to 6 and Comparative Example 1)
<Preparation of curable composition>
A polyester resin, a maleimide resin, and a catalyst were mixed and mixed by heating at the ratios shown in Table 1 to obtain a curable composition.
Maleimide resin: "BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd.
Catalyst: Dicumylperoxide

<Creation of test piece>
The curable composition obtained above was poured into a mold having a thickness of 2 mm and heated at 200 ° C. for 3 hours to be cured. Then, it was vacuum-dried by heating and stored in a room at 23 ° C. and 50% humidity for 24 hours to obtain a test piece.

<Measurement of dielectric loss tangent>
The dielectric loss tangent of the test piece at 1 GHz and 10 GHz was measured by an impedance material analyzer "HP4291B" manufactured by Agilent Technologies, Inc. in accordance with JIS-C-6481. Further, the dielectric loss tangent at 1 GHz and 10 GHz after the test piece was left under moist heat conditions (121 ° C., humidity 100%) for 6 hours was measured. In addition, the rate of change was calculated. The results are shown in Table 1.

Claims (14)

The ester compound (A) represented by the following general formula (1).

[Ar ¹ in the above general formula (1) is an aryl group which may have an independent substituent. Ar ² is an arylene group which may have a substituent independently of each other. R ¹ is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. ] Ar ¹ in the general formula (1) has an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, and 2 to 4 carbon atoms. The ester compound (A) according to claim 1, which has 1 to 3 of any one or more of alkynyloxy groups. A polyester resin containing the ester compound (A) according to claim 1 or 2. The polyester resin according to claim 3, wherein the content of the ester compound (A) is in the range of 10 to 60% as a value calculated from the area ratio of the gel permeation chromatography (GPC) chart. The polyester resin according to claim 3 or 4, which contains the ester compound (A) and the ester compound (B) represented by the following general formula (2).

[Ar ¹ in the above general formula (2) is an aryl group which may have an independent substituent. Ar ² is an arylene group which may have a substituent. ] The polyester resin according to claim 5, wherein the content of the ester compound (B) is in the range of 10 to 50% as a value calculated from the area ratio of gel permeation chromatography (GPC). A curable composition containing the ester compound (A) according to claim 1 or 2 or the polyester resin according to any one of claims 3 to 6. The curable composition according to claim 7, further comprising a maleimide compound. A cured product of the curable composition according to claim 7. A prepreg using the curable composition according to claim 7 or 8. A printed wiring board using the curable composition according to claim 7 or 8. A build-up film using the curable composition according to claim 7 or 8. A semiconductor encapsulant using the curable composition according to claim 7 or 8. A semiconductor device using the semiconductor encapsulant according to claim 13.

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