CN114671764A

CN114671764A - Ester compound and use thereof

Info

Publication number: CN114671764A
Application number: CN202111506838.4A
Authority: CN
Inventors: 金荣璨; 林弘司; 迫雅树
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2020-12-24
Filing date: 2021-12-10
Publication date: 2022-06-28
Also published as: TW202225256A; JP2022100697A

Abstract

The present invention provides an ester compound represented by the following general formula (1) and use thereof. A cured product of a curable composition using the ester compoundWhen exposed to moist heat, the dielectric loss tangent also increases little, and therefore, the resin composition can be used for prepregs, printed wiring boards, build-up films, semiconductor sealing materials, and semiconductor devices. Ar in the general formula (1)¹Each independently is an aryl group which may have a substituent. Ar (Ar)²Each independently is an arylene group which may have a substituent. R¹Is an aliphatic hydrocarbon group having 4 to 20 carbon atoms.

Description

Ester compound and use thereof

Technical Field

The present invention relates to an ester compound and use thereof, a polyester resin, a curable composition, a cured product, a prepreg, a printed wiring board, a build-up film, a semiconductor sealing material, and a semiconductor device.

Background

In recent years, electronic devices have been increasingly downsized and have high performance, and accordingly, performance of various materials used has been required to be improved. For example, in semiconductor package substrates, signals are becoming faster and higher in frequency, and there is a demand for a material having low electric energy loss, that is, a material having a low dielectric loss tangent.

As such a low dielectric loss tangent material, for example, a technique is known in which an active ester compound is used as a curing agent for an epoxy resin (see patent document 1). The epoxy resin composition described in patent document 1 has a characteristic of a lower dielectric loss tangent in a cured product than a general epoxy resin composition containing a phenol resin as a curing agent. However, moisture absorption resistance is not sufficient, and the dielectric loss tangent value greatly increases when exposed to moist heat.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2004-155990

Disclosure of Invention

[ problems to be solved by the invention ]

Accordingly, an object of the present invention is to provide a resin material which has a small increase in dielectric loss tangent when exposed to moist heat in a cured product.

[ means for solving problems ]

The present inventors have made extensive studies to solve the above problems, and as a result, have found that an ester compound having a specific molecular structure and a polyester resin containing the ester compound have a small increase in dielectric loss tangent when a cured product of the polyester resin is exposed to a moist heat condition, and have completed the present invention.

Namely, the present invention relates to an ester compound (a) represented by the following general formula (1).

[ solution 1]

[ Ar in the general formula (1)¹Each independently an aryl group which may have a substituent. Ar (Ar)²Each independently is an arylene group which may have a substituent. R¹Is 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 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 sealing material using the curable composition.

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

[ Effect of the invention ]

According to the present invention, there can be provided an ester compound, a polyester resin, a curable composition, a cured product, a prepreg, a printed wiring board, a build-up film (build film), a semiconductor sealing material, and a semiconductor device, each of which shows a small increase in dielectric loss tangent when the cured product is exposed to a moist heat condition.

Drawings

FIG. 1 is a Gel Permeation Chromatography (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.

Detailed Description

Hereinafter, a mode 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).

[ solution 2]

[ Ar in the general formula (1)¹Is an aryl group which may have a substituent. Ar (Ar)²Is an arylene group which may have a substituent. R¹Is an aliphatic hydrocarbon group having 4 to 20 carbon atoms.]

Ar in the general formula (1)¹Is an aryl group which may have a substituent. Specific examples thereof include: phenyl group, naphthyl group, and structural sites having 1 to more substituents such as halogen atom, aliphatic hydrocarbon group, alkoxy group, alkenyloxy group, alkynyloxy group, and the like on the aromatic ring thereof.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Specifically, there may be mentioned: and 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, or an alkynyl group 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, an ethynyl group, a propargyl group (propargyl), a 1-butynyl group, a 2-butynyl group, and a 3-butynyl group. Examples of the alkoxy group include methoxy, ethoxy, propoxy and butoxy. 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 an alkynyloxy group 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.

Wherein Ar is a group capable of curing the ester compound (A) alone or in combination with another polymerizable unsaturated group-containing compound such as a maleimide resin¹Preferably, the alkenyl group has at least 1 to 3 carbon atoms, and is any one or more of the alkenyl group having 2 to 4 carbon atoms, 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. At this time, the Ar¹Substituents other than these may be contained.

Ar in the general formula (1)²Is an arylene group which may have a substituent. Specific examples thereof include: phenylene group, naphthylene group, and structural sites having 1 to more substituents such as halogen atom, aliphatic hydrocarbon group, alkoxy group, alkenyloxy group, alkynyloxy group, and the like on the aromatic ring thereof. Specific examples of the halogen atom, aliphatic hydrocarbon group, alkoxy group, alkenyloxy group and alkynyloxy group include the same as those mentioned for Ar¹Examples of the substituent include the same ones as those listed above.

Wherein Ar is²Preferably, the aromatic ring of the phenylene group or the naphthylene group has 1 to 3 halogen atoms, aliphatic hydrocarbon groups, or alkoxy groups, and the phenylene group or the naphthylene group is preferred.

R in the general formula (1)¹Is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. The aliphatic hydrocarbon group may be either linear or branched, and may have an unsaturated bond in the structure. Among them, R is more remarkable in the effect of excellent dielectric characteristics in the cured product¹Preferably a linear alkylene group, and the number of carbon atoms is preferably in the range of 6 to 14.

The method for producing the ester compound (a) is not particularly limited, and examples thereof include a method in which 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) are used as reaction raw materials.

[ solution 3]

Ar¹-OH (3)

HO-R¹-OH (5)

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

Ar in the general formulae (3) to (5)¹、Ar²、R¹Specific examples and preferred examples of (3) are the same as those in the general formula (1).

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 used after being separated and purified from the reaction product, 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 directly used as the polyester resin of the present invention, other reaction raw materials may be used in combination in addition to the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its acid halide (a2), and the diol compound (a 3). In this case, in the polyester resin having more excellent dielectric characteristics in the cured product, 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) in 100 parts by mass of the reaction raw material 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.

The method for reacting 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, the ester compound (a) can be produced by a method in which the reaction raw materials are reacted in a lump, or by a multistage reaction in which a part of the reaction raw materials is reacted first and then the remaining reaction raw materials are reacted, and particularly, the ester compound (a) can be produced more efficiently, and the following method is preferable: 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 prepared in advance, and is reacted with the diol compound (a 3).

The reaction between the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) can be carried out, for example, by heating and stirring in the presence of a basic catalyst at a temperature of about 20 to 70 ℃. The reaction may be carried out in an organic solvent, if necessary. After the reaction is completed, the reaction product may be purified by washing with water, reprecipitation or the like, if necessary.

Examples of the base catalyst include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diazabicycloundecene, diazabicyclononene, and the like. They may be used alone or in combination of two or more. In addition, the aqueous solution may be used in the form of a 3 to 30 mass% aqueous solution. Among them, sodium hydroxide or potassium hydroxide having high catalytic activity is preferable. The amount of the base catalyst to be added is preferably in the range of 0.1 to 3 mol based on 1 mol of hydroxyl groups in the reaction raw material. In addition, in order to improve the reaction efficiency, an interlayer transfer catalyst such as an alkylammonium salt or crown ether (crown ether) may be used. They may be used alone or in combination of two or more. The amount of the interlayer transfer catalyst to be added is preferably in the range of 0.01 to 1% by mass based on the total mass of the reaction raw materials.

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 solvents may be used alone or in the form of a mixed solvent of two or more kinds. The amount of the organic solvent used is preferably in the range of 20 to 300% by mass based on the total mass of the reaction raw materials.

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

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

Examples of the base catalyst include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diazabicycloundecene, diazabicyclononene, and the like. They may be used alone or in combination of two or more. Further, the aqueous solution may be used in the form of an aqueous solution of about 3.0 to 30 mass%. Among them, diazabicycloundecene and diazabicyclononene having high catalytic activity are preferable. The amount of the alkali catalyst to be 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 improve the reaction efficiency, an interlayer transfer catalyst such as an alkylammonium salt or a crown ether may be used.

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 solvents may be used alone or in the form of a mixed solvent of two or more kinds.

As for the reaction ratio of the intermediate (M) to the diol compound (a3), it is preferable to use an excess amount of the intermediate (M) relative to the diol compound (a3) in terms of obtaining the ester compound (a) in 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, based on 1 mole of the diol compound (a 3).

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, as a value calculated from an area ratio in a Gel Permeation Chromatography (GPC) chart, from the viewpoint that the effect of excellent dielectric properties in a cured product is more remarkable. The upper limit value is preferably 60% or less, and more preferably 45% or less. Gel Permeation Chromatography (GPC) was measured under the measurement conditions described in examples.

Further, the polyester resin of the present invention preferably contains an ester compound (B) represented by the following general formula (2), from the viewpoint that the effect of excellent dielectric characteristics in the cured product is more remarkable. The content of the ester compound (B) in the polyester resin is preferably 10% or more, more preferably 15% or more, as calculated from an area ratio in a graph of Gel Permeation Chromatography (GPC). The upper limit value is preferably 50% or less, and more preferably 35% or less. Gel Permeation Chromatography (GPC) was measured under the measurement conditions described in examples.

[ solution 4]

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

Ar in the general formula (2)¹、Ar²Specific examples and preferred examples of (3) are the same as those in the general formula (1).

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 the ester compound (B).

[ solution 5]

[ Ar in the general formula (1)¹Each independently is an aryl group which may have a substituent. Ar (Ar)²Each independently is an arylene group which may have a substituent. R¹Is an aliphatic hydrocarbon group having 4 to 20 carbon atoms. n is an integer of 2 or more.]

Ar in the general formula (6)¹、Ar²、R¹Specific examples and preferred examples of (3) are the same as those in the general formula (1). N in the general formula (6) 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 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.

In the general formula (1), Ar is Ar having a polymerizable unsaturated group such as alkenyl group, alkynyl group, alkenyloxy group or alkynyloxy group¹Or Ar²In the case of the above substituent, the ester compound (a) of the present invention or the polyester resin containing the same may be used alone as a curable composition, or the ester compound (a) of the present invention or the polyester resin containing the same may be used as a curable composition by blending with another polymerizable unsaturated group-containing compound such as a maleimide compound. In this case, the curing reaction is generally carried out by light irradiation or heating. The heating temperature and the heating time at the time of heat curing may be appropriately adjusted depending on the formulation in the curable composition, etc., but are preferably about 1 to 24 hours at 100 to 300 ℃.

Examples of the maleimide compound include compounds represented by any one of the following general formulae (6) to (9). Further, as examples of commercially available products of maleimide resins, there can be mentioned: "BMI-1000", "BMI-2000", "BMI-2300", "BMI-3000", "BMI-4000", "BMI-6000", "BMI-7000", "BMI-8000", "BMI-TMH", etc., manufactured by Dahe chemical industry, Ltd; KI into "BMI", "BMI-70", "BMI-80", etc., manufactured by Kagaku corporation; "B1109", "N1971", "B4807", "P0778" and "P0976" manufactured by Tokyo chemical industry Co., Ltd. The maleimide compound may be used singly or in combination of two or more.

[ solution 6]

[ R in the general formula (6)²Is a divalent organic radical. R in the general formulae (7) to (9)³Is 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. X in the 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 alkylenearylenealkylene group, an oxygen atom, a sulfur atom, and a carbonyl group, and m is an integer of 1 or more. R in the general formula (8)⁴Is a hydrogen atom or an alkyl group having 1 to 4 carbon atomsAnd an aryl group. In the general formula (9), l is an integer of 3-6.]

With respect to R in the general formula (6)²Specific 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 site formed by linking two or more of these groups. Specific examples of the compound represented by the general formula (6) include: n, N '-ethylenebismaleimide, N' -hexamethylenebismaleimide, N '- (1, 3-phenylene) bismaleimide, N' - [ 1,3- (2-methylphenylene) ] -bismaleimide, N '- [ 1,3- (4-methylphenylene) ] -bismaleimide, N' - (1, 4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanebismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, N '- (1, 3-methylphenylene) -bismaleimide, N' -bismaleimido, N, bis (4-methyl-4-methylphenyl) ], bis (4-methyl-4-maleimidophenyl) methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, and their use as a pharmaceutical composition, Bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1, 4-bis (4-maleimidophenyl) cyclohexane, 1, 4-bis (maleimidomethyl) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, 1, 3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl ] methane, bis [4- (4-maleimidophenoxy) phenyl ] methane, 1-bis [4- (3-maleimidophenoxy) phenyl ] ethane, 1-bis [4- (4-maleimidophenoxy) phenyl ] ethane, bis (4-maleimidocyclohexyl) methane, bis (4-maleimidomethyl) benzene, bis (4-maleimidophenoxy) benzene, bis (3-maleimidophenoxy) phenyl) ethane, bis (4-maleimidophenoxy) methyl) benzene, bis (4-methyl) ethyl-methyl) ethyl acetate, bis (4-methyl) ethyl acetate, bis (maleimidophenyl) acetate, bis (4-methyl) acetate, bis (maleimidophenyl) acetate, bis (4-acetate, bis (maleimidophenyl) acetate, bis (2-acetate, bis (maleimide) acetate, bis (4-acetate, bis (maleimide) acetate, bis (4-acetate, bis (maleimide) acetate, bis (2), and (maleimide) acetate, bis (4-acetate, bis (2), and (maleimide) acetate, bis (4-acetate, bis (2), bis (maleimide) acetate, bis (2), and (maleimide) acetate, bis (4-acetate, bis (2) acetate, bis (maleimide) acrylate, bis (2), and (2) acrylate, bis (2), and (2) acrylate, bis (maleimide) acrylate, bis (2), and (maleimide) acrylate, bis (2) acrylate, bis (4-acrylate, bis (maleimide) acrylate, bis (2) acrylate, bis (maleimide) acrylate, 1, 2-bis [4- (3-maleimidophenoxy) phenyl ] ethane, 1, 2-bis [4- (4-maleimidophenoxy) phenyl ] ethane, 2-bis [4- (3-maleimidophenoxy) phenyl ] propane, 2-bis [4- (4-maleimidophenoxy) phenyl ] propane, 2-bis [4- (3-maleimidophenoxy) phenyl ] butane, 2-bis [4- (4-maleimidophenoxy) phenyl ] butane, 2-bis [ (4- (3-maleimidophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 2-bis [4- (4-maleimidophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, 4-bis (3-maleimidophenoxy) biphenyl, 4-bis (4-maleimidobenzene) Oxy) biphenyl, bis [ 4- (3-maleimidophenoxy) phenyl ] ketone, bis [ 4- (4-maleimidophenoxy) phenyl ] ketone, 2' -bis (4-maleimidophenyl) disulfide, bis [ 4- (3-maleimidophenoxy) phenyl ] disulfide, 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- (3-maleimidophenoxy) phenyl ] sulfone, Bis [ 4- (4-maleimidophenoxy) phenyl ] ether, 1, 4-bis [ 4- (4-maleimidophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 3-bis [ 4- (4-maleimidophenoxy) - α 0, α 1-dimethylbenzyl ] benzene, 1, 4-bis [ 4- (3-maleimidophenoxy) - α 2, α 3-dimethylbenzyl ] benzene, 1, 3-bis [ 4- (3-maleimidophenoxy) - α 4, α 5-dimethylbenzyl ] benzene, 1, 4-bis [ 4- (4-maleimidophenoxy) -3, 5-dimethyl- α, α -dimethylbenzyl ] benzene, 1, 4-bis [ 4- (4-maleimidophenoxy) - α, α -dimethylbenzyl ] benzene, or mixtures thereof, 1, 3-bis [ 4- (4-maleimidophenoxy) -3, 5-dimethyl-. alpha.,. alpha. -dimethylbenzyl ] benzene, 1, 4-bis [ 4- (3-maleimidophenoxy) -3, 5-dimethyl-. alpha.,. alpha. -dimethylbenzyl ] benzene, 1, 3-bis [ 4- (3-maleimidophenoxy) -3, 5-dimethyl-. alpha.,. alpha. -dimethylbenzyl ] benzene, 4-methyl-1, 3-phenylenebismaleimide, polyphenylmethanemaleimide and the like.

When the ester compound (a) or the polyester resin containing the same of the present invention has a polymerizable unsaturated group, the ratio of the ester compound (a) or the polyester resin containing the same to the total mass of the compounds having a polymerizable unsaturated group in the curable composition is not particularly limited, and can be appropriately adjusted depending on the desired resin performance, use, and the like. The proportion of the ester compound (a) or the polyester resin containing the same 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 still more preferably in the range of 30 to 60% by mass.

The ester compound (a) and the polyester resin containing the same of the present invention have an ester bond between aromatic rings in the structure, and therefore function as a so-called active ester compound or resin, and thus can be used as a curable composition by blending with an epoxy resin or the like. In this case, the hardening reaction is generally carried out by heating. The heating temperature and the heating time may be appropriately adjusted depending on the formulation of the curable composition, etc., but are preferably about 1 to 24 hours at 100 to 300 ℃. The curable composition of the present invention may contain both a compound containing a polymerizable unsaturated group such as the above maleimide compound and an epoxy resin.

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, phenol biphenyl aralkyl type epoxy resins and the like; bisphenol type epoxy resins such as 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, tetrabromobisphenol a type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyl oxybenzene skeleton; naphthalene type epoxy resins; binaphthol type epoxy resins; a binaphthyl-type epoxy resin; dicyclopentadiene type epoxy resins such as dicyclopentadiene phenol type epoxy resins; glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, and glycidyl amine type epoxy resin of diaminodiphenylsulfone; diglycidyl ester type epoxy resins such as 2, 6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin and glycidyl ester type epoxy resin of hexahydrophthalic anhydride; and benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. They may be used alone or in combination of two or more.

When the curable composition of the present invention contains the above epoxy resin, the ester compound (a) of the present invention or a curing agent for an epoxy resin other than the polyester resin may be used in combination. Examples of the curing agent for epoxy resin include an active ester resin other than the ester compound (a) and the polyester resin of the present invention, an amine compound, an amide compound, an acid anhydride, a phenol resin, a cyanate resin, and a benzoxazine resin.

When the curable composition of the present invention contains the epoxy resin, the proportion of the epoxy resin to be blended with the ester compound (a), the polyester resin, or the other curing agent for epoxy resin of the present invention is preferably 0.7 to 1.5 moles of the total of the functional groups in the curing agent, based on 1 mole of the total of the epoxy groups in the curable composition.

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.

Examples of the phosphorus-based hardening accelerator include: organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-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 tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide salt, butylphenyl phosphonium dicyanamide salt, tetrabutylphosphonium decanoate salt and the like.

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

Examples of the imidazole-based hardening accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-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-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-dimethylimidazole, 2-ethylimidazole, 2-ethyliodonium trimellitate, 2-phenylimidazolium trimellitate, 2-dimethylimidazole, 2-methyl-imidazole, 1-ethyl-2-methyl-imidazole, 2-methyl-ethyl-methyl-imidazole, 2-methyl-ethyl-imidazole, 2-methyl-ethyl-methyl-ethyl-methyl-2-methyl-ethyl-2-methyl-ethyl-methyl-imidazole, or-2-ethyl-methyl-2-methyl-ethyl-2-ethyl-methyl-2-methyl-one, 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.

Examples of the guanidine-based hardening 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, 1-phenylbiguanide and the like.

Examples of the urea-based hardening accelerator include: 3-phenyl-1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, chlorophenylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, and the like.

As the peroxide, there may be mentioned: dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, azobisisobutyronitrile, and the like.

Among the hardening accelerators, dicumyl peroxide, 2-ethyl-4-methylimidazole and dimethylaminopyridine are preferably used.

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

Examples of the flame retardant include: inorganic phosphorus compounds such as ammonium phosphates and phosphoric acid amides, including red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; organic phosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane (phosphine) compounds, organic nitrogen-containing phosphorus compounds, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, cyclic organic phosphorus compounds such as 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting these organic phosphorus compounds with compounds such as epoxy resins and phenol resins; nitrogen flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; silicone 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, they are preferably contained in the curable resin composition in a range of 0.1 to 20% by mass.

The inorganic filler is prepared, for example, when the curable resin composition of the present invention is used for a semiconductor sealing material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, the fused silica is preferable in that more inorganic filler can be blended. The fused silica may be in a crushed form or a spherical form, but in order to increase the amount of the fused silica and to suppress an increase in the melt viscosity of the curable composition, it is preferable to use mainly spherical silica. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

When the curable composition of the present invention is used for an electrically conductive paste or the like, an electrically 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 or a build-up adhesive film, it is generally preferable to use the composition after mixing and diluting with an organic solvent. Examples of the organic solvent include: methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, and the like. The type and amount of the organic solvent may be appropriately adjusted depending on the use environment of the curable composition, and for example, in the case of printed wiring board use, polar solvents having a boiling point of 160 ℃ or less such as methyl ethyl ketone, acetone, dimethylformamide, and cyclohexanone are preferably used in a proportion such that the nonvolatile content is 25 to 80 mass%. For the application to the build-up adhesive film, it is preferable to use a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone, an acetate solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, a carbitol solvent such as cellosolve, butyl carbitol, an aromatic hydrocarbon solvent such as toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or the like, and it is preferable to use them in a proportion such that the nonvolatile content is 25 to 60 mass%.

The curable composition of the present invention can be used for manufacturing a printed wiring board by, for example, impregnating a reinforcing base material with the curable composition, curing the composition to obtain a prepreg, laminating the prepreg with a copper foil, and thermally pressing the prepreg. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, and the like. The impregnation amount of the curable composition is not particularly limited, and it is generally preferable to prepare the curable composition so that the resin component in the prepreg is 20 to 60 mass%.

When the curable composition of the present invention is used for a semiconductor sealing material, it is generally preferable to blend an inorganic filler. The semiconductor sealing material can be prepared by mixing the formulation using, for example, an extruder, a kneader, a roll, or the like. A method for molding a semiconductor package using the obtained semiconductor sealing material includes, for example, a method in which the semiconductor sealing material is molded using a casting, transfer molding, injection molding, or the like, and further heated at a temperature of 50 to 200 ℃ for 2 to 10 hours, whereby a semiconductor device as a molded product can be obtained.

[ examples ]

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

< measurement conditions of Gel Permeation Chromatography (GPC) >)

A measuring device: HLC-8320GPC manufactured by Tosoh corporation,

Pipe column: protective column "HXL-L" manufactured by Tosoh corporation "

"TSK-GEL G4000 HXL" manufactured by Tosoh corporation "

"TSK-GEL G3000 HXL" manufactured by Tosoh corporation "

"TSK-GEL G2000 HXL", manufactured by Tosoh corporation "

A detector: RI (differential refractometer)

Data processing: "GPC workstation EcoSEC-word Station" manufactured by Tosoh corporation "

The measurement conditions were as follows: the temperature of the column is 40 DEG C

Developing solvent tetrahydrofuran

Flow rate 1.0 ml/min

The standard is as follows: the following monodisperse polystyrene having a known molecular weight was used according to the manual for measurement of "GPC-8320".

(use of polystyrene)

"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 preparation: a sample (50. mu.l) obtained by filtering a tetrahydrofuran solution at 1.0 mass% in terms of resin solid content was filtered using a microfilter.

＜¹³Measurement Condition of C-NMR

The device comprises the following steps: JNM-ECA500 manufactured by Japan electronic products Ltd "

Measurement mode: inverse gated decoupling (inverted gated decoupling)

Solvent: deuterated dimethyl sulfoxide

Pulse angle: 30 deg. pulse

Sample concentration: 30% by mass

And (4) accumulating times: 4,000 times

Standard of chemical shift: peak of dimethyl sulfoxide: 39.5ppm of

< determination of FD-MS >

The FD-MS was measured using a double focusing (double focusing) type mass spectrometer "AX 505H (FD 505H)" manufactured by japan electronics corporation.

Example 1 production of polyester resin (1)

A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 101.0g of isophthalic acid chloride and 397.0g of toluene, and the inside of the system was dissolved by replacing it with nitrogen under reduced pressure. Then, 134.0g of 2-allylphenol was charged, and the inside of the system was dissolved by replacing the pressure with nitrogen under reduced pressure. Further, 0.30g of tetrabutylammonium bromide was added thereto and dissolved. While purging with nitrogen, the temperature in the system was controlled to 60 ℃ or lower, and 206.0g of a 20% aqueous solution of sodium hydroxide was added dropwise over a period of 3 hours. Stirring was continued for 1.0 hour under the same temperature conditions. After the reaction, the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was poured into the toluene layer containing the reactant dissolved therein, and the mixture was stirred and mixed for about 15 minutes, followed by standing for liquid separation and removal of the water layer. This operation was repeated until the pH of the aqueous layer became 7. Then, water and toluene were removed by decantation and dehydration to obtain a liquid intermediate (1). Carbon spectrum nuclear magnetic resonance of intermediate (1) (1) ¹³C-nuclear magnetic resonance，¹³C-NMR) chart is shown in fig. 1, FD-MS chart is shown in fig. 2, and GPC chart is shown in fig. 3.

A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 60.0g of 1, 9-nonanediol, 298.4g of the intermediate (1), and 1.79g of Diazabicycloundecene (DBU). After the inside of the system was replaced with nitrogen under reduced pressure, the temperature was raised to 190 ℃ and the mixture was stirred at the same temperature for 3 hours. Thereafter, 2-allylphenol was removed by distillation under reduced pressure to obtain a polyester resin (1). The weight average molecular weight (Mw) of the polyester resin (1), calculated from the area ratio in the graph of Gel Permeation Chromatography (GPC), was 1,848. The content of the ester compound (a) in the polyester resin (1) was 29% and the content of the ester compound (B) was 21%, as calculated from the area ratio in the graph of Gel Permeation Chromatography (GPC). The GPC diagram of the polyester resin (1) is shown in fig. 1.

Example 2 production of polyester resin (2)

A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 40.0g of 1, 6-hexanediol, 249.5g of the intermediate (1), and 1.45g of Diazabicycloundecene (DBU). After the inside of the system was replaced with nitrogen under reduced pressure, the temperature was raised to 190 ℃ and the mixture was stirred at the same temperature for 3.5 hours. Thereafter, 2-allylphenol was removed by distillation under reduced pressure to obtain a polyester resin (2). The weight average molecular weight (Mw) of the polyester resin (2) calculated from the area ratio in the graph of Gel Permeation Chromatography (GPC) was 1,489. The content of the ester compound (a) in the polyester resin (2) was 28% and the content of the ester compound (B) was 21%, as calculated from the area ratio in the graph of Gel Permeation Chromatography (GPC). The GPC diagram of the polyester resin (2) is shown in fig. 2.

Example 3 production of polyester resin (3)

A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer was charged with 50.0g of 1, 12-dodecanediol, 208.74g of the intermediate (1), and 1.29g of Diazabicycloundecene (DBU). After the inside of the system was replaced with nitrogen under reduced pressure, the temperature was raised to 190 ℃ and the mixture was stirred at the same temperature for 7 hours. Thereafter, 2-allylphenol was removed by distillation under reduced pressure to obtain a polyester resin (3). The weight average molecular weight (Mw) of the polyester resin (3), calculated from the area ratio in the chart of Gel Permeation Chromatography (GPC), was 1,647. The content of the ester compound (a) in the polyester resin (3) was 32% and the content of the ester compound (B) was 26%, as calculated from the area ratio in the graph of Gel Permeation Chromatography (GPC). The GPC chart of the polyester resin (3) is shown in fig. 3.

(examples 4 to 6 and comparative example 1)

< preparation of curable composition >

A curable composition was obtained by blending a polyester resin, a maleimide resin and a catalyst in the proportions shown in Table 1 and heating and mixing them.

Maleimide resin: "BMI-5100" manufactured by Dahe chemical industry Co., Ltd "

Catalyst: dicumyl peroxide

< preparation of test piece >

The curable composition thus obtained was poured into a mold frame having a thickness of 2mm, and heated at 200 ℃ for 3 hours to cure the composition. Thereafter, the dried product was dried under vacuum and heated, and stored at 23 ℃ and a humidity of 50% for 24 hours to obtain a test piece.

< measurement of dielectric loss tangent >

The dielectric loss tangent at 1GHz and 10GHz of the test piece was measured by using an impedance material analyzer (HP 4291B) "manufactured by Agilent Technologies, Inc., in accordance with Japanese Industrial Standards (JIS) -C-6481. Further, the dielectric loss tangent at 1GHz and 10GHz after the test piece was left to stand under moist heat conditions (121 ℃ C., humidity 100%) for 6 hours was measured. In addition, the rate of change thereof is calculated. The results are shown in table 1.

[ Table 1]

Claims

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

ar in the general formula (1)¹Each independently an aryl group which may have a substituent; ar (Ar)²Each independently is an arylene group which may have a substituent; r¹Is an aliphatic hydrocarbon group having 4 to 20 carbon atoms.

2. The ester compound (A) according to claim 1, wherein Ar in the general formula (1) ¹Has 1-3 alkenyl groups having 2-4 carbon atoms, alkynyl groups having 2-4 carbon atoms, alkenyloxy groups having 2-4 carbon atoms, and alkynyloxy groups having 2-4 carbon atoms.

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

4. 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 an area ratio in a graph of Gel Permeation Chromatography (GPC).

5. The polyester resin according to claim 3 or 4, comprising the ester compound (A) and an ester compound (B) represented by the following general formula (2),

ar in the general formula (2)¹Each independently an aryl group which may have a substituent; ar (Ar)²Is an arylene group which may have a substituent.

6. 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 an area ratio of Gel Permeation Chromatography (GPC).

7. A curable composition comprising the ester compound (A) according to claim 1 or 2 or the polyester resin according to any one of claims 3 to 6.

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

9. A cured product of the curable composition according to claim 7.

10. A prepreg using the curable composition according to claim 7 or 8.

11. A printed wiring board using the curable composition according to claim 7 or 8.

12. A build-up film using the curable composition according to claim 7 or 8.

13. A semiconductor sealing material using the curable composition according to claim 7 or 8.

14. A semiconductor device using the semiconductor sealing material according to claim 13.