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

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

[Technical field]

[0001] The present invention relates to an ester compound, 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. [Background technology]

[0002] In recent years, electronic devices have become smaller and more powerful, and the performance requirements for the various materials used in them are improving accordingly. For example, in semiconductor package substrates, signals are becoming faster and higher in frequency, and materials with low electrical energy loss, i.e., low dielectric tangent, are required.

[0003] As such a material with a low dielectric 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 of a low dielectric tangent in the cured product compared to a general epoxy resin composition using a phenolic resin as a curing agent. However, the moisture absorption resistance is insufficient, and the dielectric tangent value increases significantly when exposed to moist and hot conditions. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2004-155990 A Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, an object of the present invention is to provide a resin material which, in its cured form, exhibits a small increase in dielectric tangent when exposed to moist heat conditions. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems and discovered that an ester compound having a specific molecular structure and a polyester resin containing the same show only a small increase in dielectric tangent when a cured product thereof is exposed to moist heat conditions, thereby completing the present invention.

[0007] That is, the present invention relates to an ester compound (A) represented by the following general formula (1).

[0008] [ka] [Ar in the above general formula (1)] 1 Each of Ar is independently an aryl group which may have a substituent. 2 R is an arylene group which may have a substituent. 1 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms.

[0009] The present invention further relates to a polyester resin containing the ester compound (A).

[0010] The present invention further relates to a curable composition containing the ester compound (A) or the polyester resin.

[0011] The present invention further relates to a cured product of the curable composition.

[0012] The present invention further relates to a prepreg using the curable composition.

[0013] The present invention further relates to a printed wiring board using the curable composition.

[0014] The present invention further relates to a build-up film using the curable composition.

[0015] The present invention further relates to a semiconductor encapsulant using the curable composition.

[0016] The present invention further relates to a semiconductor device using a semiconductor encapsulant made of the above curable composition. Effect of the Invention

[0017] According to the present invention, it is possible to provide an ester compound, 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, which have a small increase in dielectric tangent when the cured product is exposed to moist heat conditions. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a GPC chart of the polyester resin (1) obtained in Example 1. [Diagram 2] FIG. 2 is a GPC chart of the polyester resin (2) obtained in Example 2. [Diagram 3] FIG. 3 is a GPC chart of the polyester resin (3) obtained in Example 3. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Hereinafter, an embodiment of 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).

[0020] [ka] [Ar in the above general formula (1)] 1 is an aryl group which may have a substituent. 2 R is an arylene group which may have a substituent. 1 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms.

[0021] In the general formula (1), Ar 1is an aryl group which may have a substituent. Specific examples thereof include a phenyl group, a naphthyl group, and structural moieties having one or more substituents such as a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, or an alkynyloxy group on the aromatic ring of the phenyl group, naphthyl group, or the like.

[0022] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The aliphatic hydrocarbon group may be either a straight-chain type or a branched type, and may have an unsaturated bond in the structure. Specific examples include alkyl groups 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; alkenyl groups having 2 to 4 carbon atoms, such as a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group; and alkyl groups having 2 to 4 carbon atoms, such as an ethynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, and a 3-butynyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butyloxy group. Examples of the alkenyloxy group include alkenyloxy groups 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 alkynyloxy groups having 2 to 4 carbon atoms, such as an ethynyloxy group, a propargyloxy group, a 1-butynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group.

[0023] Among these, the ester compound (A) can undergo a curing reaction alone or in combination with other polymerizable unsaturated group-containing compounds such as maleimide resins. 1 It is preferable that Ar has at least 1 to 3 of at least one of the alkenyl groups having 2 to 4 carbon atoms, the alkynyl groups having 2 to 4 carbon atoms, the alkenyloxy groups having 2 to 4 carbon atoms, and the alkynyloxy groups having 2 to 4 carbon atoms. 1 may have a substituent other than those mentioned above.

[0024] In the general formula (1), Ar2 is an arylene group which may have a substituent. Specific examples thereof include a phenylene group, a naphthylene group, and structural moieties having one or more substituents such as a halogen atom, an aliphatic hydrocarbon group, an alkoxy group, an alkenyloxy group, or an alkynyloxy group on the aromatic ring of these groups. Specific examples of the halogen atom, the aliphatic hydrocarbon group, the alkoxy group, the alkenyloxy group, and the alkynyloxy group include the above-mentioned Ar 1 Examples of the substituent include the same as those given above.

[0025] Among them, Ar 2 is preferably a phenylene group, a naphthylene group, or a structural moiety having, on an aromatic ring thereof, 1 to 3 of at least one of a halogen atom, an aliphatic hydrocarbon group, and an alkoxy group, and is preferably a phenylene group or a naphthylene group.

[0026] R in the general formula (1) 1 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. The aliphatic hydrocarbon group may be either a straight chain type or a branched type, and may have an unsaturated bond in the structure. Among them, R 1 is preferably a linear alkylene group having 6 to 14 carbon atoms.

[0027] The method for producing the ester compound (A) is not particularly limited, and an example thereof includes a method using, as reaction raw materials, a phenolic hydroxyl group-containing compound (a1) represented by the following structural formula (3), an aromatic dicarboxylic acid or an acid halide thereof (a2) represented by the following general formula (4), and a diol compound (a3) ​​represented by the following structural formula (5).

[0028] [ka] [Ar in the above general formula (3)] 1 is an aryl group which may have a substituent. 2R in the general formula (5) is an arylene group which may have a substituent. 1 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms.

[0029] In the general formulas (3) to (5), Ar 1 , Ar 2 , R 1 Specific examples and preferred ones are the same as those in the general formula (1).

[0030] When the polyester 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), by-products other than the ester compound (A) may be generated in the reaction product. 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.

[0031] 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 the polyester resin of the present invention, the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its acid halide (a2), and the diol compound (a3) ​​may be used in combination with other reaction raw materials. In that case, the polyester resin has better dielectric properties in the cured product, so that the total mass of the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its acid halide (a2), and the diol compound (a3) ​​per 100 parts by mass of the reaction raw materials of the polyester resin 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.

[0032] 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 may be produced by a method of reacting the reaction raw materials all at once, or may be produced by a multi-stage reaction in which a part of the reaction raw materials is reacted first and the remaining reaction raw materials are reacted thereafter. In particular, the ester compound (A) can be produced more efficiently by a method in which an intermediate (M), which is an ester of the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2), is produced in advance, and then the intermediate is reacted with the diol compound (a3).

[0033] The reaction of the phenolic hydroxyl group-containing compound (a1) with the aromatic dicarboxylic acid or its acid halide (a2) can be carried out, for example, in the presence of an alkali catalyst by heating and stirring at a temperature of about 20 to 70° C. The reaction may be carried out in an organic solvent as necessary. After completion of the reaction, the reaction product may be purified by washing with water, reprecipitation, or the like, as desired.

[0034] Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diazabicycloundecene, and diazabicyclononene. These may be used alone or in combination of two or more. They may also be used as an aqueous solution of 3 to 30% by mass. Among them, sodium hydroxide or potassium hydroxide, which has high catalytic activity, is preferred. The amount of the alkali catalyst added is preferably in the range of 0.1 to 3 moles per mole of hydroxyl groups in the reaction raw material. In addition, in order to increase the reaction efficiency, a phase transfer catalyst such as an alkyl ammonium salt or a crown ether may be used. These may be used alone or in combination of two or more. The amount of the return 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.

[0035] Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, carbitol solvents such as cellosolve and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in the form of 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 based on the total mass of the reaction raw materials.

[0036] The reaction ratio of the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) is preferably in the range of 0.8 to 3 mol, more preferably 1.5 to 2.2 mol, of the phenolic hydroxyl group-containing compound (a1) per 1 mol of the aromatic dicarboxylic acid or its acid halide (a2), in order to obtain the ester compound (A) in a higher yield.

[0037] The reaction of the intermediate (M), which is an ester of the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2), with the diol compound (a3) ​​can be carried out, for example, in the presence of an alkali catalyst, by heating and stirring at a temperature of about 50 to 250°C. The reaction may be carried out in an organic solvent as necessary. After the reaction is completed, it is preferable to distill off the phenolic hydroxyl group-containing compound (a1) produced as a result of the transesterification reaction. In addition, the reaction product may be purified by washing with water, reprecipitation, or the like, as desired.

[0038] Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diazabicycloundecene, and diazabicyclononene. These may be used alone or in combination of two or more. They may also be used as an aqueous solution of about 3.0 to 30%. Among them, diazabicycloundecene and diazabicyclononene, which have high catalytic activity, are preferred. The amount of the alkali catalyst added is preferably in the range of 0.01 to 10% by mass based on the total mass of the reaction raw materials. In addition, in order to increase the reaction efficiency, an interphase transfer catalyst such as an alkyl ammonium salt or a crown ether may be used.

[0039] Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitol solvents such as cellosolve, butyl carbitol, etc., aromatic hydrocarbon solvents such as toluene, xylene, etc., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. These may be used alone or in the form of a mixed solvent of two or more kinds.

[0040] The reaction ratio of the intermediate (M) and the diol compound (a3) ​​is preferably such that the intermediate (M) is used in excess relative to the diol compound (a3) ​​in order to obtain the ester compound (A) in a higher yield. Specifically, the intermediate (M) is preferably used in an amount of 1.1 to 5 moles, more preferably 1.5 to 4 moles, and even more preferably 1.8 to 3 moles, relative to 1 mole of the diol compound (a3).

[0041] The content of the ester compound (A) in the polyester resin of the present invention is preferably 10% or more, more preferably 15% or more, calculated from the area ratio of the chart of gel permeation chromatography (GPC), since the effect of excellent dielectric properties in the cured product becomes more remarkable. The upper limit is preferably 60% or less, more preferably 45% or less. The gel permeation chromatography (GPC) was measured under the measurement conditions described in the examples.

[0042] Furthermore, the polyester resin of the present invention preferably contains an ester compound (B) represented by the following general formula (2), since the effect of excellent dielectric properties in the cured product becomes more pronounced. The content of the ester compound (B) in the polyester resin is preferably 10% or more, more preferably 15% or more, as calculated from the area ratio of a gel permeation chromatography (GPC) chart. The upper limit is preferably 50% or less, more preferably 35% or less. The gel permeation chromatography (GPC) was measured under the measurement conditions described in the Examples. [ka] [Ar in the above general formula (2)] 1 Each of Ar is independently an aryl group which may have a substituent. 2 represents an arylene group which may have a substituent.

[0043] In the general formula (2), Ar 1 , Ar 2 Specific examples and preferred ones are the same as those in the general formula (1).

[0044] The polyester resin of the present invention may contain an ester compound (C) represented by the following general formula (6), in addition to the ester compound (A) and ester compound (B).

[0045] [ka] [Ar in the above general formula (1)] 1 Each of Ar is independently an aryl group which may have a substituent. 2 R is an arylene group which may have a substituent. 1 is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. n is an integer of 2 or more.

[0046] In the general formula (6), Ar 1 , Ar 2 , R 1 Specific examples and preferred ones 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.

[0047] The number average molecular weight (Mn) of the polyester resin of the present invention is preferably in the range of 500 to 5,000, and 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, and more preferably in the range of 800 to 5,000. In this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyester resin are measured using gel permeation chromatography (GPC) under the measurement conditions described in the Examples.

[0048] In the general formula (1), Ar 1 Or Ar 2 When the above substituent has a polymerizable unsaturated group such as an alkenyl group, an alkynyl group, an alkenyloxy group, or an alkynyloxy group, the ester compound (A) of the present invention or a polyester resin containing the ester compound (A) can be used as a curable composition by itself or by blending with other polymerizable unsaturated group-containing compounds such as a maleimide compound. In this case, the curing reaction generally proceeds by light irradiation or heating. The heating temperature and heating time during heat curing are appropriately adjusted depending on the blending components in the curable composition, but it is preferably about 100 to 300 ° C for 1 to 24 hours.

[0049] Examples of the maleimide compound include those represented by any one 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", "BMI-6000", "BMI-7000", "BMI-8000", and "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd., "BMI", "BMI-70", and "BMI-80" manufactured by K.I. Kasei Co., Ltd., and "B1109", "N1971", "B4807", "P0778", and "P0976" manufactured by Tokyo Kasei Kogyo Co., Ltd. The maleimide compound may be used alone or in combination of two or more kinds.

[0050] [ka] [R in the above general formula (6)] 2 R in the above general formulas (7) to (9) is a divalent organic group. 3 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 of 0 to 3. In the above general formula (7), X 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 alkylenearylenealkylene group, an oxygen atom, a sulfur atom, and a carbonyl group, and m is an integer of 1 or more. 4 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.]

[0051] R in the general formula (6) 2Regarding the above, specific examples of the divalent organic group include an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 6 to 20 carbon atoms, an arylene group, an oxygen atom, a sulfur atom, a carbonyl group, and a structural portion in which two or more of these groups are linked together.Specific examples of the compound represented by the general formula (6) include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, 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-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3, 3-Dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenyl) midophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-Hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, 2,2'-bis(4-maleimidophenyl)disulfide, bis(4-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4- (4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4- Bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 4-methyl-1,3-phenylene bismaleimide, polyphenylmethane maleimide, etc.

[0052] When the ester compound (A) of the present invention or the polyester resin containing the ester compound (A) has a polymerizable unsaturated group, the ratio of the ester compound (A) or the polyester resin containing the ester compound (A) to the total mass of the compounds having a polymerizable unsaturated group in the curable composition is not particularly limited and is appropriately adjusted according to the desired resin performance, use, etc. Among them, 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 compounds having a polymerizable unsaturated group in the curable composition is preferably 20% by mass or more, more preferably in the range of 25 to 75% by mass, and particularly preferably in the range of 30 to 60% by mass.

[0053] The ester compound (A) of the present invention and the polyester resin containing the same have an ester bond between aromatic rings in the structure, and therefore function as a so-called active ester compound or resin, and can be used as a curable composition by blending with an epoxy resin or the like. In this case, the curing reaction generally proceeds by heating. The heating temperature and heating time are appropriately adjusted depending on the blending components in the curable composition, but are preferably 100 to 300°C for about 1 to 24 hours. The curable composition of the present invention may contain both the polymerizable unsaturated group-containing compound such as the maleimide compound and the epoxy resin.

[0054] The epoxy resin is not particularly limited, and examples thereof include novolac type epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, α-naphthol novolac type epoxy resins, β-naphthol novolac type epoxy resins, bisphenol A novolac type epoxy resins, and biphenyl novolac type epoxy resins; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, and phenol biphenyl aralkyl type epoxy resins; and bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol AP type epoxy resins, bisphenol AF type epoxy resins, bisphenol B type epoxy resins, bisphenol BP type epoxy resins, bisphenol C type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and tetrabromobisphenol A type epoxy resins. Examples of the epoxy resins include biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton; naphthalene-type epoxy resins; binaphthol-type epoxy resins; binaphthyl-type epoxy resins; dicyclopentadiene-type epoxy resins such as dicyclopentadienephenol-type epoxy resins; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone-type glycidylamine-type epoxy resins; diglycidyl ester-type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester-type epoxy resins and hexahydrophthalic anhydride-type glycidyl ester-type epoxy resins; and benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These may be used alone or in combination of two or more.

[0055] When the curable composition of the present invention contains the epoxy resin, a curing agent for 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) of the present invention or the polyester resin, amine compounds, amide compounds, acid anhydrides, phenolic resins, cyanate ester resins, and benzoxazine resins.

[0056] When the curable composition of the present invention contains the epoxy resin, the blending ratio of the ester compound (A) of the present invention or the polyester resin and other epoxy resin curing agents is preferably such that the total amount of functional groups in the curing agent is 0.7 to 1.5 mol per 1 mol of the epoxy groups in the curable composition.

[0057] 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 release agent, a pigment, and an emulsifier, if necessary.

[0058] The curing accelerator is not particularly limited, but 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.

[0059] Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-para-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethyl phosphite and triethyl phosphite; and phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, and tetrabutylphosphonium decanoate.

[0060] Examples of the amine curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU), and 1,5-diazabicyclo[4.3.0]-nonene-5 (DBN).

[0061] Imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 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, and 1-cyanoethyl-2-ethyl-4-methylimidazole. undecyl-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-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and the like.

[0062] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, and 1-phenylbiguanide.

[0063] Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

[0064] Examples of the peroxide include dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, and azobisisobutyronitrile.

[0065] Of the above-mentioned curing accelerators, it is preferable to use dicumyl peroxide, 2-ethyl-4-methylimidazole, and dimethylaminopyridine.

[0066] The above-mentioned curing accelerators may be used alone or in combination of two or more kinds.

[0067] The amount of the curing accelerator used is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the resin solid content of the curable composition. When the amount of the curing accelerator used is 0.01 part by mass or more, it is preferable because the curing properties are 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.

[0068] Examples of the flame retardant include inorganic phosphorus compounds such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides; phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. , 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and other cyclic organic phosphorus compounds, and derivatives thereof reacted with compounds such as epoxy resins and phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, the content of the flame retardants in the curable resin composition is preferably in the range of 0.1 to 20 mass %.

[0069] 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, and aluminum hydroxide. Among them, the fused silica is preferred because it allows more inorganic filler to be blended. The fused silica can be used in either crushed or spherical form, but it is preferred to mainly use spherical silica in order to increase the blending amount of fused silica and suppress the increase in the melt viscosity of the curable composition. Furthermore, in order to increase the blending amount of spherical silica, it is preferred to appropriately adjust the particle size distribution of the spherical silica. It is preferred to blend the filler in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

[0070] In addition, when the curable composition of the present invention is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

[0071] When the curable composition of the present invention is used for printed wiring boards or build-up adhesive films, it is generally preferred to dilute the composition 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, and propylene glycol monomethyl ether acetate. The type and amount of the organic solvent can be appropriately adjusted depending on the environment in which the curable composition is used. For example, in printed wiring board applications, it is preferred to use polar solvents with a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, dimethylformamide, and cyclohexanone, and it is preferred to use the organic solvent at a ratio of 25 to 80% by mass of non-volatile content. For build-up adhesive film applications, it is preferable to use ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc.; acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.; carbitol solvents such as cellosolve, butyl carbitol, etc.; aromatic hydrocarbon solvents such as toluene, xylene, etc.; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use them in a proportion such that the non-volatile content is 25 to 60 mass%.

[0072] In addition, a method for producing a printed wiring board using the curable composition of the present invention includes, for example, a method in which the curable composition is impregnated into a reinforcing substrate, cured to obtain a prepreg, and then the prepreg and copper foil are laminated and heated and pressed together. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The amount of impregnation of the curable composition is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60 mass%.

[0073] When the curable composition of the present invention is used as a semiconductor encapsulation material, it is generally preferred to add an inorganic filler. The semiconductor encapsulation material can be prepared by mixing the compound using, for example, an extruder, a kneader, a roll, etc. A method for molding a semiconductor package using the obtained semiconductor encapsulation material includes, for example, molding the semiconductor encapsulation material using a casting or transfer molding machine, an injection molding machine, etc., and further heating the material at a temperature of 50 to 200°C for 2 to 10 hours. By such a method, a semiconductor device, which is a molded product, can be obtained. EXAMPLES

[0074] The present invention will now be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these.

[0075] <Gel Permeation Chromatography (GPC) Measurement Conditions> Measurement equipment: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + "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: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the above-mentioned "GPC-8320," the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A 1.0 mass% tetrahydrofuran solution in terms of resin solid content, filtered through a microfilter (50 μl)

[0076] < 13 Measurement conditions for C-NMR Apparatus: "JNM-ECA500" manufactured by JEOL Ltd. Measurement mode: Inverse-gated decoupling Solvent: Deuterated dimethyl sulfoxide Pulse angle: 30° pulse Sample concentration: 30 mass% Number of accumulations: 4,000 times Reference for chemical shift: Peak of dimethyl sulfoxide: 39.5 ppm

[0077] <Measurement of FD-MS FD-MS was measured using a double-focusing mass spectrometer "AX505H (FD505H)" manufactured by JEOL Ltd.

[0078] (Example 1: Production of polyester resin (1)) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 101.0 g of isophthalic acid chloride and 397.0 g of toluene were charged, and the inside of the system was substituted with nitrogen under reduced pressure to dissolve. Next, 134.0 g of 2-allylphenol was charged, and the inside of the system was substituted with nitrogen under reduced pressure to dissolve. 0.30 g of tetrabutylammonium bromide was further added and dissolved. While purging with nitrogen gas, the inside of the system was controlled to 60°C or less, and 206.0 g of 20% aqueous sodium hydroxide solution was dropped over 3 hours. Stirring was continued under the same temperature conditions for 1.0 hour. After the reaction was completed, the mixture was left to stand for separation, and the aqueous layer was removed. Water was added to the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was left to stand for separation to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. After that, water and toluene were removed by decanter dehydration to obtain a liquid intermediate (1). Intermediate (1) 13 The C-NMR chart is shown in Figure 1, the FD-MS chart in Figure 2, and the GPC chart in Figure 3.

[0079] In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 60.0 g of 1,9-nonanediol, 298.4 g of the intermediate (1), and 1.79 g of diazabicycloundecene (DBU) were charged. After the system was purged with nitrogen under reduced pressure, the temperature was raised to 190°C and stirred at the same temperature for 3 hours. Then, 2-allylphenol was removed by distillation under reduced pressure to obtain polyester resin (1). The weight average molecular weight (Mw) of polyester resin (1) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 1,848. In addition, the content of ester compound (A) in polyester resin (1) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 29%, and the content of ester compound (B) was 21%. The GPC chart of polyester resin (1) is shown in Figure 1.

[0080] (Example 2: Production of polyester resin (2)) 40.0 g of 1,6-hexanediol, 249.5 g of the intermediate (1), and 1.45 g of diazabicycloundecene (DBU) were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. After the system was purged with nitrogen under reduced pressure, the temperature was raised to 190°C and stirred at the same temperature for 3.5 hours. Then, 2-allylphenol was removed by distillation under reduced pressure to obtain polyester resin (2). The weight average molecular weight (Mw) of polyester resin (2) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 1,489. In addition, the content of ester compound (A) in polyester resin (2) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 28%, and the content of ester compound (B) was 21%. The GPC chart of polyester resin (2) is shown in Figure 2.

[0081] (Example 3: Production of polyester resin (3)) 50.0 g of 1,12-dodecanediol, 208.74 g of the intermediate (1), and 1.29 g of diazabicycloundecene (DBU) were charged into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. After the system was purged with nitrogen under reduced pressure, the temperature was raised to 190°C and stirred at the same temperature for 7 hours. Then, 2-allylphenol was removed by distillation under reduced pressure to obtain polyester resin (2). The weight average molecular weight (Mw) of polyester resin (3) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 1,647. In addition, the content of ester compound (A) in polyester resin (3) calculated from the area ratio of the gel permeation chromatography (GPC) chart was 32%, and the content of ester compound (B) was 26%. The GPC chart of polyester resin (3) is shown in Figure 3.

[0082] (Examples 4 to 6 and Comparative Example 1) <Preparation of Curable Composition> The polyester resin, maleimide resin, and catalyst were mixed in the ratios shown in Table 1 and heated to obtain a curable composition. Maleimide resin: "BMI-5100" manufactured by Daiwa Chemical Industry Co., Ltd. Catalyst: Dicumyl peroxide

[0083] <Creating test pieces> The curable composition obtained above was poured into a 2 mm thick mold and heated at 200°C for 3 hours to be cured. After that, it was heated and vacuum dried, and stored in a room at 23°C and 50% humidity for 24 hours to obtain a test piece.

[0084] <Measurement of dielectric tangent> In accordance with JIS-C-6481, the dielectric tangent of the test piece was measured at 1 GHz and 10 GHz using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies. The dielectric tangent of the test piece was also measured at 1 GHz and 10 GHz after it was left under humid heat conditions (121°C, 100% humidity) for 6 hours. The rate of change was also calculated. The results are shown in Table 1.

[0085] [Table 1]

Claims

1. An ester compound (A) represented by the following general formula (1): 【Chemistry 1】 [Ar in the above general formula (1)] １ Ar is an aryl group having 1 to 3 of at least one of 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 an alkynyloxy group having 2 to 4 carbon atoms. ２ R each independently represents an arylene group which may have a substituent. １ is an aliphatic hydrocarbon group having 4 to 20 carbon atoms.

2. A polyester resin comprising the ester compound (A) according to claim 1.

3. 3. The polyester resin according to claim 2, wherein the content of the ester compound (A) is in the range of 10 to 60%, as calculated from the area ratio in a gel permeation chromatography (GPC) chart.

4. The polyester resin according to claim 2 or 3, comprising the ester compound (A) and an ester compound (B) represented by the following general formula (2): 【Chemistry 2】 [Ar in the above general formula (2)] １ Each of Ar is an aryl group which may have a substituent. ２ represents an arylene group which may have a substituent.

5. 5. The polyester resin according to claim 4, wherein the content of the ester compound (B) is in the range of 10 to 50% as calculated from the area ratio of gel permeation chromatography (GPC).

6. A curable composition comprising the ester compound (A) according to claim 1 or the polyester resin according to any one of claims 2 to 5.

7. The curable composition according to claim 6 , further comprising a maleimide compound.

8. A cured product of the curable composition according to claim 6.

9. A prepreg using the curable composition according to claim 6 or 7.

10. A printed wiring board using the curable composition according to claim 6 or 7.

11. A build-up film using the curable composition according to claim 6 or 7.

12. A semiconductor encapsulant using the curable composition according to claim 6 or 7.

13. A semiconductor device using the semiconductor encapsulation material according to claim 12.

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