TWI903003B - Polyester resins, curable compounds, cured materials, prepregs, printed wiring boards, laminates, semiconductor sealing materials, and semiconductor devices. - Google Patents

Abstract

This invention provides an ester compound represented by the following general formula (1). The cured composition of the curable compound using said ester compound exhibits a small increase in dielectric loss tangent even when exposed to humid and hot conditions, and therefore can be used in prepregs, printed wiring boards, laminates, semiconductor sealing materials, and semiconductor devices.

In the general formula (1), ^Ar1 is an aryl group that can have substituents. ^Ar2 is an aryl group that can have substituents. ^R1 is an aliphatic hydrocarbon with 4 to 20 carbon atoms.

Description

Polyester resins, curing compounds, cured materials, prepregs, printed circuit board substrates, laminates, semiconductor sealing materials, and semiconductor devices

This invention relates to an ester compound, polyester resin, curable composition, cured material, prepreg, printed wiring substrate, laminate, semiconductor sealing material, and semiconductor device.

In recent years, the miniaturization and high performance of electronic devices have continued to advance, leading to higher performance requirements for various materials used. For example, in semiconductor packaging substrates, the increasing speed and frequency of signals necessitate the development of materials with low power loss, i.e., materials with low dielectric loss tangent.

As for materials with such low dielectric loss tangents, techniques for using reactive ester compounds as curing agents for epoxy resins are known (see Patent 1). The epoxy resin composition described in Patent 1 exhibits a lower dielectric loss tangent in the cured product compared to general epoxy resin compositions using phenolic resins as curing agents. However, its moisture resistance is not sufficient; the dielectric loss tangent increases significantly when exposed to humid and hot conditions.

[Existing technical literature] [Patent Documents]

[Patent Document 1] Japanese Patent Application Publication No. 2004-155990

Therefore, the problem to be solved by this invention is to provide a resin material with a small rise in dielectric loss tangent when exposed to humid and hot conditions in the cured material.

The inventors and others conducted intensive research to solve the aforementioned problem, and as a result discovered that in ester compounds with specific molecular structures and polyester resins containing said ester compounds, the increase in dielectric loss tangent is small when the cured polyester resin is exposed to humid and hot conditions, thus completing the present invention.

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

[In the general formula (1), ^Ar1 is an aryl group that may have substituents. ^Ar2 is an aryl group that may have substituents. ^R1 is an aliphatic hydrocarbon with 4 to 20 carbon atoms.]

This invention further relates to a polyester resin containing the aforementioned ester compound (A).

This invention further relates to a curing composition comprising the ester compound (A) or the polyester resin.

This invention further relates to a hardened form of the aforementioned hardening composition.

This invention further relates to a prepreg using the aforementioned curing composition.

This invention further relates to a printed wiring substrate using the aforementioned curing composition.

This invention further relates to a thickening film using the aforementioned curing composition.

This invention further relates to a semiconductor sealing material using the aforementioned hardening composition.

This invention further relates to a semiconductor device that uses a semiconductor sealing material utilizing the aforementioned hardening composition.

According to the present invention, ester compounds, polyester resins, curable compositions, curables, prepregs, printed wiring substrates, buildup films, semiconductor sealing materials, and semiconductor devices can be provided, exhibiting a small increase in dielectric loss tangent when their cured contents are exposed to humid and hot conditions.

Figure 1 is a gel permeation chromatography (GPC) chart of the polyester resin (1) obtained in Example 1.

Figure 2 is a GPC chart of the polyester resin (2) obtained in Example 2.

Figure 3 is a GPC chart of the polyester resin (3) obtained in Example 3.

The following is a detailed description of the methods used to implement this invention.

The ester compound (A) of this invention is characterized by being represented by the following general formula (1).

[In the general formula (1), ^Ar1 is an aryl group that may have substituents. ^Ar2 is an aryl group that may have substituents. ^R1 is an aliphatic hydrocarbon with 4 to 20 carbon atoms.]

Ar ¹ in the general formula (1) is an aryl group that may have substituents. Specific examples include: phenyl, naphthyl, and structural sites having one or more halogen atoms, aliphatic hydrocarbons, alkoxy groups, alkenoxy groups, alkynoxy groups, alkynoxy groups, etc., on their aromatic rings.

Examples of halogen atoms include fluorine, chlorine, and bromine atoms. The aliphatic hydrocarbon group can be either linear or branched, and may contain unsaturated bonds in its structure. Specifically, examples include alkyl groups with 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; alkenyl groups with 2 to 4 carbon atoms such as vinyl, allyl, 1-butenyl, 2-butenyl, and 3-butenyl; and alkynyl groups with 2 to 4 carbon atoms such as ethynyl, propargyl, 1-butynyl, 2-butynyl, and 3-butynyl. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy. The alkenyloxy group, for example, includes vinyloxy, allyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, and other alkenyloxy groups having 2 to 4 carbon atoms. The alkynyloxy group, for example, includes ethynyloxy, propynyloxy, 1-butynyloxy, 2-butynyloxy, 3-butynyloxy, and other alkynyloxy groups having 2 to 4 carbon atoms.

Wherein, for the ester compound (A) to undergo a curing reaction alone or to undergo a curing reaction with other compounds containing polymerizable unsaturated groups such as maleimide resin, the Ar ¹ is preferably at least one to three alkenyl groups having 2 to 4 carbon atoms, alkynyl groups having 2 to 4 carbon atoms, alkenoxy groups having 2 to 4 carbon atoms, and alkynoxy groups having 2 to 4 carbon atoms. In this case, the Ar ¹ may also have other substituents.

In the general formula (1), ^Ar2 is an aryl group that may have substituents. Specific examples include: arylphenyl, arylnaphthyl, and structural sites having one or more halogen atoms, aliphatic hydrocarbons, alkoxy groups, alkenoxy groups, alkynoxy groups, etc., on their aromatic rings. Specific examples of halogen atoms, aliphatic hydrocarbons, alkoxy groups, alkenoxy groups, and alkynoxy groups include groups that are the same as those listed as examples of substituents on ^Ar1 .

Ar ² is preferably an enantylphenyl, an enantynyl, or a structural site having one or more of one to three halogen atoms, aliphatic hydrocarbons, or alkoxy groups on its aromatic ring, preferably an enantylphenyl or an enantynyl.

In the general formula (1), ^R1 is an aliphatic hydrocarbon with 4 to 20 carbon atoms. The aliphatic hydrocarbon can be either linear or branched, and may also have unsaturated bonds in its structure. Among these, ^R1 is preferably a linear alkyl group with a carbon number preferably in the range of 6 to 14, which is more significant in terms of improving the dielectric properties of the cured material.

The method for producing the ester compound (A) is not particularly limited. For example, a method using a compound containing a phenolic hydroxyl group (a1) represented by structural formula (3), an aromatic dicarboxylic acid or its acid halogenated form (a2) represented by general formula (4), and a diol compound (a3) represented by structural formula (5) as reactants can be cited.

[In general formula (3) ^{, Ar1} is an aryl group that may have substituents. In general formula (4), ^Ar2 is an exynaryl group that may have substituents. In general formula (5) ^{, R1} is an aliphatic hydrocarbon with 4 to 20 carbon atoms.]

The specific examples and preferred embodiments of ^Ar1 , ^Ar2 , and ^R1 in general formulas (3) to (5) are the same as those in general formula (1).

During the production of the polyester compound (A) from the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its halogenated form (a2), and the diol compound (a3), byproducts other than the ester compound (A) are sometimes generated in the reaction products. In this invention, the ester compound (A) can be separated and purified from the reaction products for use, or the reaction products can be used as the polyester resin of this invention.

When the reaction product of the phenolic hydroxyl-containing compound (a1), the aromatic dicarboxylic acid or its acid halogenated derivative (a2), and the diol compound (a3) is directly used as the polyester resin of the present invention, other reactants besides the phenolic hydroxyl-containing compound (a1), the aromatic dicarboxylic acid or its acid halogenated derivative (a2), and the diol compound (a3) may also be used. In this case, for the purpose of obtaining a polyester resin with superior dielectric properties in the cured product, the total mass of the phenolic hydroxyl-containing compound (a1), the aromatic dicarboxylic acid or its acid halogenated derivative (a2), and the diol compound (a3) in 100 parts by mass of the reactants 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 reaction method for the phenolic hydroxyl group-containing compound (a1), the aromatic dicarboxylic acid or its acid halogenated derivative (a2), and the diol compound (a3) is not particularly limited. For example, it can be produced by reacting the reactants uniformly, or by a multi-stage reaction, such as reacting a portion of the reactants first and then the remaining reactants. Particularly for more efficient production of the ester compound (A), a preferred method is to pre-prepare an intermediate (M) as an esterification of the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halogenated derivative (a2), and then react it with the diol compound (a3).

The reaction of the phenolic hydroxyl group-containing compound (a1) with the aromatic dicarboxylic acid or its acid halogenate (a2) can be carried out, for example, by heating and stirring in the presence of an alkaline catalyst at a temperature of approximately 20°C to 70°C. Alternatively, the reaction can be carried out in an organic solvent, if desired. After the reaction, the reaction products can be purified, if necessary, by washing with water or reprecipitation.

Examples of alkaline catalysts include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diazabis(bicycloundecene), and diazabis(bicyclononene). They can be used individually or in combination of two or more. Alternatively, they can be used as an aqueous solution of 3% to 30% by mass. Sodium hydroxide or potassium hydroxide, which have high catalytic activity, are preferred. The amount of alkaline catalyst added is preferably in the range of 0.1 to 3 mol relative to 1 mol of hydroxyl in the reactants. Furthermore, to improve reaction efficiency, interlayer moving catalysts such as alkyl ammonium salts or crown ethers can be used. They can be used individually or in combination of two or more. The optimal addition amount of interlayer moving catalyst relative to the total mass of the reactants is 0.01% to 1% by mass.

The organic solvents mentioned include, for example, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, solvent acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as solvents and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. They can be used individually or in mixtures of two or more solvents. The preferred amount of these organic solvents relative to the total mass of the reactants is 20% to 300% by mass.

Regarding the reaction ratio of the phenolic hydroxyl-containing compound (a1) to the aromatic dicarboxylic acid or its acid halogenate (a2) to obtain the ester compound (A) in higher yield, it is preferably that the ratio of the phenolic hydroxyl-containing compound (a1) is in the range of 0.8 mol to 3 mol, more preferably 1.5 mol to 2.2 mol, relative to 1 mol of the aromatic dicarboxylic acid or its acid halogenate (a2).

The reaction of the intermediate (M) of the esterification product of the phenolic hydroxyl group-containing compound (a1) and the aromatic dicarboxylic acid or its acid halogenate (a2) with the diol compound (a3) can be carried out, for example, by heating and stirring in the presence of an alkaline catalyst at a temperature of approximately 50°C to 250°C. Alternatively, the reaction can be carried out in an organic solvent if desired. After the reaction, it is preferable to dilute the phenolic hydroxyl group-containing compound (a1) produced as a result of the esterification reaction. Alternatively, the reaction products can be purified by washing with water or reprecipitation if necessary.

Examples of the alkaline catalysts include sodium hydroxide, potassium hydroxide, triethylamine, triphenylamine, pyridine, imidazole, diaza-bis(undecane), and diaza-bis(nonene). They can be used individually or in combination of two or more. Alternatively, they can be used as an aqueous solution of approximately 3.0% to 30% by mass. Diaza-bis(undecane) and diaza-bis(nonene), which have high catalytic activity, are preferred. The amount of alkaline catalyst added relative to the total mass of the reactants is preferably in the range of 0.01% to 10% by mass. Furthermore, to improve reaction efficiency, interlayer moving catalysts such as alkyl ammonium salts or crown ethers can also be used.

The organic solvents mentioned include, for example, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, solvent acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol solvents such as solvents and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. They can be used individually or in mixtures of two or more solvents.

Regarding the reaction ratio of the intermediate (M) to the diol compound (a3), to obtain the ester compound (A) in higher yield, it is preferable to use an excess of the intermediate (M) relative to the diol compound (a3). Specifically, it is preferable to use 1.1 mol to 5 mol of the intermediate (M) relative to 1 mol of the diol compound (a3), more preferably 1.5 mol to 4 mol, and even more preferably 1.8 mol to 3 mol.

Regarding the significantly superior dielectric properties of the cured material, the content of the ester compound (A) in the polyester resin of the present invention, calculated based on the area ratio in a gel osmosis chromatography (GPC) chart, is preferably 10% or more, more preferably 15% or more. Furthermore, the upper limit is preferably 60% or less, more preferably 45% or less. Moreover, the gel osmosis chromatography (GPC) is performed under the measurement conditions described in the embodiments.

Furthermore, regarding the more significant effect of superior dielectric properties in the cured material, the polyester resin of the present invention preferably contains an ester compound (B) represented by the following general formula (2). The content of the ester compound (B) in the polyester resin, calculated based on the area ratio in a gel osmosis chromatography (GPC) chart, is preferably 10% or more, more preferably 15% or more. Additionally, its upper limit is preferably 50% or less, more preferably 35% or less. Moreover, the gel osmosis chromatography (GPC) is performed under the measurement conditions described in the embodiments.

[In the general formula (2), ^Ar1 is an aryl group that may have substituents. ^Ar2 is an aryl group that may have substituents.]

The specific examples and preferred forms of Ar ¹ and Ar ² in the general formula (2) are the same as those in the general formula (1).

In addition to the ester compounds (A) and (B) described above, the polyester resin of this invention may also contain the ester compound (C) represented by the following general formula (6).

[In the general formula (1), ^Ar1 is an aryl group that may have substituents. ^Ar2 is an aryl group that may have substituents. ^R1 is an aliphatic hydrocarbon with 4 to 20 carbon atoms. n is an integer of 2 or more.]

The specific examples and preferred forms of ^Ar1 , ^Ar2 , and ^R1 in the general formula (6) are the same as those in the general formula (1). In the general formula (6), n is an integer greater than 2, and more preferably an integer from 2 to 10.

The number average molecular weight (Mn) of the polyester resin of this invention is preferably in the range of 500 to 5,000, more preferably in the range of 600 to 3,000. Furthermore, 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 this specification, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyester resin are determined using gel osmosis chromatography (GPC) under the determination conditions described in the embodiments.

When a polymerizable unsaturated group such as alkenyl, alkynyl, alkenyloxy, or alkynyloxy is used as a substituent on ^Ar1 or ^Ar2 in the general formula (1), the ester compound (A) of the present invention or a polyester resin containing it can be used alone as a curing compound, or the ester compound (A) of the present invention or a polyester resin containing it can be used as a curing compound by blending with other compounds containing polymerizable unsaturated groups such as maleimide compounds. In this case, the curing reaction is generally carried out by light irradiation or heating. The heating temperature and heating time during heat curing can be appropriately adjusted according to the blending components in the curing compound, but it is preferred to heat at 100°C to 300°C for about 1 hour to 24 hours.

The maleimide compounds mentioned above may include compounds represented by any of the following general formulas (6) to (9). Examples of commercially available maleimide resins include: "BMI-1000", "BMI-2000", "BMI-2300", "BMI-3000", "BMI-4000", "BMI-6000", "BMI-7000", "BMI-8000", and "BMI-TMH" manufactured by Daiwa Chemical Industries, Ltd.; "BMI", "BMI-70", and "BMI-80" manufactured by KI Chemical Industries, Ltd.; and "B1109", "N1971", "B4807", "P0778", and "P0976" manufactured by Tokyo Chemical Industries, Ltd. The maleimide compound may be used alone or in combination with two or more.

[In general formula (6) ^{, R2} is a divalent organic group. In general formulas (7) to (9) ^{, R3} is any one of alkyl, halogen, alkoxy, aryl, or aralkyl with 1 to 8 carbon atoms, and n is an integer from 0 to 3. In general formula (7), X is any one of alkyl, cycloalkyl, aryl, alkylarylalkylalkyl, oxygen, sulfur, or carbonyl with 1 to 6 carbon atoms, and m is an integer greater than or equal to 1. In general formula (8), ^R4 is any one of hydrogen, alkyl, or aryl with 1 to 4 carbon atoms. In general formula (9), 1 is an integer from 3 to 6.]

Regarding ^R2 in the general formula (6), specific examples of divalent organic groups include alkyl groups with 1 to 6 carbon atoms, cycloalkyl groups with 6 to 20 carbon atoms, aryl groups, oxygen atoms, sulfur atoms, carbonyl groups, and structural sites formed by the linkage of two or more of these groups. Specific examples of compounds represented by the general formula (6) include, for example: N,N'-epenylethyl bismaleimide, N,N'-hexaethyl bismaleimide, N,N'-(1,3-epenylphenyl) bismaleimide, N,N'-[1,3-(2-methylepenylphenyl)] bismaleimide, N,N'-[1,3-(4-methylepenylphenyl)] bismaleimide, N,N'-(1,4-epenylphenyl) bismaleimide, bis(4-maleimidephenyl)methyl Alkane, bis(3-methyl-4-maleiminophenyl)methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane, bismaleimide, bis(4-maleiminophenyl) ether, bis(4-maleiminophenyl) sulfide, bis(4-maleiminophenyl) ketone, bis(4-maleiminocyclohexyl)methane, 1,4-bis(4-maleiminophenyl)cyclohexane, 1,4-bis(maleiminomethyl)cyclohexane, 1,4 - bis(maleiminomethyl)benzene, 1,3-bis(4-maleiminophenoxy)benzene, 1,3-bis(3-maleiminophenoxy)benzene, bis[4-(3-maleiminophenoxy)phenyl]methane, bis[4-(4-maleiminophenoxy)phenyl]methane, 1,1-bis[4-(3-maleiminophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleiminophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleiminophenoxy)phenyl] [Phenyl]ethane, 1,2-bis[4-(4-maleiminophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleiminophenoxy)phenyl]propane, 2,2-bis[4-(4-maleiminophenoxy)phenyl]propane, 2,2-bis[4-(3-maleiminophenoxy)phenyl]butane, 2,2-bis[4-(4-maleiminophenoxy)phenyl]butane, 2,2-bis[[4-(3-maleiminophenoxy)phenyl]-1,1,1,3] 3,3-Hexafluoropropane, 2,2-bis[4-(4-maleiminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleiminophenoxy)biphenyl, 4,4-bis(4-maleiminophenoxy)biphenyl, bis[4-(3-maleiminophenoxy)phenyl]one, bis[4-(4-maleiminophenoxy)phenyl]one, 2,2'-bis(4-maleiminophenyl)disulfide, bis(4-maleiminophenyl)di Thioethers, bis[4-(3-maleiminophenoxy)phenyl] disulfide, bis[4-(4-maleiminophenoxy)phenyl] sulfide, bis[4-(3-maleiminophenoxy)phenyl] ione, bis[4-(4-maleiminophenoxy)phenyl] ione, bis[4-(3-maleiminophenoxy)phenyl] ione, bis[4-(4-maleiminophenoxy)phenyl] ione, bis[4-(3-maleiminophenoxy)phenyl] ether, bis[4-(4-maleiminophenoxy)phenyl] ether [Oxyphenyl] ether, 1,4-bis[4-(4-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleiminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleiminophenoxy)-3,5-dimethyl]benzene Examples of benzyl-α,α-dimethylbenzylbenzene, 1,3-bis[4-(4-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzylbenzene, 1,4-bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzylbenzene, 1,3-bis[4-(3-maleiminophenoxy)-3,5-dimethyl-α,α-dimethylbenzylbenzene, 4-methyl-1,3-epylphenylbismaleimide, polyphenylmethanemaleimide, etc.

When the ester compound (A) of the present invention or the polyester resin containing it has polymerizable unsaturated groups, the mass ratio of the ester compound (A) or the polyester resin containing it to the total mass of the compounds having polymerizable unsaturated groups in the curing composition is not particularly limited, and can be appropriately adjusted according to the desired resin properties or applications. Preferably, the mass ratio of the ester compound (A) or the polyester resin containing it to the total mass of the compounds having polymerizable unsaturated groups in the curing composition per 100 parts by mass is 20% by mass or more, more preferably in the range of 25% to 75% by mass, and even more preferably in the range of 30% to 60% by mass.

The ester compound (A) and the polyester resin containing it of this invention have ester bonds between aromatic rings in their structure, thus functioning as a so-called active ester compound or resin. Therefore, by formulation with epoxy resins, they can be used as curing compounds. In this case, the curing reaction is generally carried out by heating. The heating temperature and heating time can be appropriately adjusted according to the formulation components in the curing compound, but it is preferred to heat at 100°C to 300°C for approximately 1 hour to 24 hours. Furthermore, the curing compound of this invention may also contain both the aforementioned maleimide compound and other compounds containing polymerizable unsaturated groups, as well as epoxy resins.

There are no particular limitations on the epoxy resins mentioned, and examples include: phenolic varnish-type epoxy resins, cresol varnish-type epoxy resins, α-naphthol varnish-type epoxy resins, β-naphthol varnish-type epoxy resins, bisphenol A varnish-type epoxy resins, biphenyl varnish-type epoxy resins, and other phenolic varnish-type epoxy resins; phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, etc. Aryl alkyl epoxy resins such as phenol-biphenyl aralkyl type epoxy resins; 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, etc.; Biphenyl-type epoxy resins, including tetramethylbiphenyl-type epoxy resins and epoxy resins with a biphenyl backbone and a diglycidyloxybenzene backbone; naphthyl-type epoxy resins; binaphthol-type epoxy resins; binaphthyl-type epoxy resins; dicyclopentadiene-type epoxy resins; tetraglycidyldiaminodiphenylmethane-type epoxy resins; triglycidyl-p-amino-type epoxy resins; Glyceryl amine type epoxy resins, such as phenolic epoxy resins and diaminodiphenyl phosphate epoxy resins; diglyceryl ester type epoxy resins, such as 2,6-naphthalenedicarboxylic acid diglyceryl ester type epoxy resins and hexahydrophthalic anhydride diglyceryl ester type epoxy resins; benzopyran type epoxy resins, such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These can be used individually or in combination.

In the case where the curing composition of the present invention contains the epoxy resin, a curing agent for epoxy resins other than the ester compound (A) of the present invention or polyester resins may also be used. Examples of curing agents for epoxy resins include, for example, active ester resins other than the ester compound (A) of the present invention or polyester resins, or amine compounds, amide compounds, acid anhydrides, phenolic resins, cyanate ester resins, benzoxazine resins, etc.

When the curing composition of the present invention contains the epoxy resin, the mixing ratio of the curing agent with the ester compound (A) or polyester resin, or other epoxy resin, is preferably 1 mol relative to the total number of epoxy groups in the curing composition, and the total number of functional groups in the curing agent is 0.7 to 1.5 mol.

The curing composition of this invention may also contain various additives such as curing accelerators, flame retardants, inorganic fillers, silane coupling agents, mold release agents, pigments, and emulsifiers, as needed.

There are no particular limitations on the types of hardening accelerators mentioned, and examples include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, urea-based hardening accelerators, peroxides, azo compounds, etc.

Examples of phosphorus-based hardening accelerators include: organophosphorus compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organophosphite compounds such as trimethylphosphite and triethylphosphite; and phosphite salts such as ethyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, butylphosphine tetraphenylborate, tetraphenylphosphine tetraphenylborate, tetraphenylphosphine tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphine thiocyanate, tetraphenylphosphine dicyanamide, butylphenylphosphine dicyanamide, and tetrabutylphosphine decanoate.

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

Examples of 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, 1-cyano... Ethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, etc.

Examples of guanidine-based sclerosis promoters 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-methylbiguanidine, 1-ethylbiguanidine, 1-butylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, and 1-phenylbiguanidine.

Examples of urea-based sclerosis accelerators 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.

Examples of such peroxides include: dicumyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl peroxide, diisopropyl peroxide, di-2-ethylhexyl peroxide, and azobisisobutyronitrile.

The preferred hardening accelerators are dicumyl peroxide, 2-ethyl-4-methylimidazole, and dimethylaminopyridine.

Furthermore, the hardening accelerator can be used alone or in combination of two or more.

Regarding the amount of curing accelerator used, relative to 100 parts by weight of the resin solid content of the curing compound, it is preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight. When the amount of curing accelerator used is 0.01 parts by weight or more, the curing properties are excellent, and therefore preferred. On the other hand, when the amount of curing accelerator used is 5 parts by weight or less, the formability is excellent, and therefore preferred.

The flame retardants may include, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and other inorganic phosphorus compounds such as ammonium phosphate and amide phosphate; phosphate ester compounds, phosphonic acid compounds, phosphine derivatives, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphenanthroline-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphenanthroline-10-oxide, 10-(2, Organophosphorus compounds, including cyclic organophosphorus compounds such as (7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and their derivatives formed by reacting these organophosphorus compounds with epoxy resins or phenolic resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine compounds; silicone-based flame retardants such as silicone oil, silicone rubber, and silicone resins; and inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting-point glasses. When using these flame retardants, the preferred concentration is in the range of 0.1% to 20% by mass in the curing resin composition.

The inorganic filler material is formulated, for example, in the case where the curable resin composition of the present invention is used as a semiconductor sealing material. Examples of the inorganic filler material include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, fused silica is preferred for allowing for the formulation of a larger quantity of inorganic filler material. The fused silica can be either crushed or spherical, but to increase the amount of fused silica and suppress the increase in the melt viscosity of the curable composition, it is preferable to primarily use spherical silica. Furthermore, to increase the amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. Regarding its filling ratio, it is preferably formulated in the range of 0.5 to 95 parts by weight per 100 parts by weight of the curing resin composition.

Furthermore, when using the curable composition of this invention for applications such as conductive paste, conductive fillers such as silver powder or copper powder can be used.

When using the curable composition of the present invention for printed wiring board applications or as an additive bonding film, it is generally preferred to dilute it with an organic solvent before use. Examples of such organic solvents include: methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl solvent, ethyl glycol acetate, propylene glycol monomethyl ether acetate, etc. The type and amount of organic solvent can be adjusted appropriately according to the application environment of the curable composition. For example, in printed wiring board applications, polar solvents with a boiling point below 160°C, such as methyl ethyl ketone, acetone, dimethylformamide, and cyclohexanone, are preferred, and it is preferred to use them at a ratio of 25% to 80% by mass of non-volatile components. In applications involving thickened adhesive films, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone are preferred; ethyl acetate, butyl acetate, solvent acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and other acetate solvents are also preferred; carbitol solvents such as butyl carbitol are preferred; aromatic hydrocarbon solvents such as toluene and xylene are preferred; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are also preferred. It is preferable to use these solvents at a non-volatile content of 25% to 60% by weight.

Furthermore, a method for manufacturing a printed wiring substrate using the curable composition of this invention can be exemplified by impregnating a reinforcing substrate with the curable composition and curing it to obtain a prepreg blank, which is then overlapped with copper foil and heat-pressed. The reinforcing substrate can be, for example, paper, glass cloth, glass nonwoven fabric, aromatic polyamide paper, aromatic polyamide cloth, glass felt, glass roving, etc. The impregnation amount of the curable composition is not particularly limited, but it is generally preferred to prepare the prepreg with a resin content of 20% to 60% by mass.

When using the hardening composition of this invention as a semiconductor sealing material, it is generally preferred to formulate an inorganic filler material. The semiconductor sealing material can be prepared, for example, using an extruder, kneader, roller, or other mixing and compounding method. Methods for molding semiconductor packages using the obtained semiconductor sealing material include, for example, molding the semiconductor sealing material using a casting or transfer molding machine, injection molding machine, etc., and then heating it at a temperature of 50°C to 200°C for 2 to 10 hours. Through this method, a semiconductor device as a molded product can be obtained.

[Implementation Example]

The invention will now be described in more detail using embodiments and comparative examples, but the invention is not limited to these.

<Determination conditions for gel osmosis chromatography (GPC)>

Measurement device: HLC-8320 GPC manufactured by Tosoh Corporation

Tube String: Protective tube string "HXL-L" manufactured by Tosoh Corporation

+TSK-GEL G4000HXL manufactured by Tosoh Corporation

+TSK-GEL G3000HXL manufactured by Tosoh Corporation

+TSK-GEL G2000HXL manufactured by Tosoh Corporation

+TSK-GEL G2000HXL manufactured by Tosoh Corporation

Detector: RI (Differential Refractometer)

Data processing: "GPC EcoSEC-Work Station" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40℃

Development solvent tetrahydrofuran

Flow rate: 1.0 ml/min

Standard: According to the "GPC-8320" testing manual, using monodisperse polystyrene with a known molecular weight as described below.

(Using polystyrene)

The "A-500" manufactured by Tosoh Corporation

The "A-1000" manufactured by Tosoh Corporation

The "A-2500" manufactured by Tosoh Corporation

The "A-5000" manufactured by Tosoh Corporation

The F-1 fighter jet manufactured by Tosoh Corporation.

The F-2 manufactured by Tosoh Corporation

The F-4 manufactured by Tosoh Corporation

The F-10 manufactured by Tosoh Corporation

The F-20 manufactured by Tosoh Corporation

The F-40 manufactured by Tosoh Corporation

The F-80 manufactured by Tosoh Corporation

The F-128 manufactured by Tosoh Corporation

Sample: A 50 μl sample obtained by filtering a tetrahydrofuran solution with a resin solids content of 1.0% by mass using a microfilter.

< ¹³ C-NMR Measurement Conditions>

Measurement mode: Inverse gated decoupling

Solvent: Deuterated dimethyl sulfoxide

Pulse angle: 30° pulse

Sample concentration: 30% by mass

Total number of times: 4,000

Chemical shift benchmark: peak for dimethyl monoxide: 39.5 ppm

<FD-MS Measurement>

FD-MS was performed using the "AX505H (FD505H)" double-focusing mass analyzer manufactured by Nippon Electronics Co., Ltd.

(Example 1: Manufacturing of polyester resin (1))

101.0 g of isophthalic acid chloroform and 397.0 g of toluene were added to a flask equipped with a thermometer, dropping funnel, coolant, separator, and stirrer. The system was then purged with reduced-pressure nitrogen to dissolve them. Next, 134.0 g of 2-allylphenol was added, and the system was purged with reduced-pressure nitrogen to dissolve it. Then, 0.30 g of tetrabutylammonium bromide was added to dissolve it. While purging with nitrogen and maintaining the system temperature below 60°C, 206.0 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. The mixture was stirred continuously for 1 hour at the same temperature. After the reaction was complete, the mixture was allowed to stand and separated, and the aqueous layer was removed. Water was added to the toluene layer containing the reactants and stirred for about 15 minutes. The mixture was then allowed to stand and separated, and the aqueous layer was removed. This process was repeated until the pH of the aqueous layer reached 7. Subsequently, water and toluene were removed by dehydration to obtain a liquid intermediate (1). The ^13C -NMR spectrum of the intermediate ( ¹ ) is shown in Figure 1, the FD-MS spectrum is shown in Figure 2, and the GPC spectrum is shown in Figure 3.

60.0 g of 1,9-nonanediol, 298.4 g of the intermediate (1), and 1.79 g of diazabicycloundecene (DBU) were added to a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. After purging the system with depressurized nitrogen, the temperature was raised to 190°C and stirred at the same temperature for 3 hours. Subsequently, 2-allylphenol was removed by depressurized distillation to obtain polyester resin (1). The weight-average molecular weight (Mw) of polyester resin (1), calculated from the area ratio in the gel osmosis chromatography (GPC) chart, was 1,848. Furthermore, based on the area ratios calculated from the gel osmosis chromatography (GPC) chart, the content of ester compound (A) in polyester resin (1) is 29%, and the content of ester compound (B) is 21%. The GPC chart of polyester resin (1) is shown in Figure 1.

(Example 2: Manufacturing 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 added to a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. After purging the system with depressurized nitrogen, the temperature was raised to 190°C and stirred at the same temperature for 3.5 hours. Subsequently, 2-allylphenol was removed by depressurized distillation to obtain polyester resin (2). The weight-average molecular weight (Mw) of polyester resin (2), calculated from the area ratio in the gel osmosis chromatography (GPC) chart, was 1,489. Furthermore, based on the area ratios calculated from the gel osmosis chromatography (GPC) chart, the content of ester compound (A) in polyester resin (2) is 28%, and the content of ester compound (B) is 21%. The GPC chart of polyester resin (2) is shown in Figure 2.

(Example 3: Manufacturing 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 added to a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. After purging the system with depressurized nitrogen, the temperature was raised to 190°C and stirred for 7 hours at the same temperature. Subsequently, 2-allylphenol was removed by depressurized distillation to obtain polyester resin (3). The weight-average molecular weight (Mw) of polyester resin (3), calculated from the area ratio in the gel osmosis chromatography (GPC) chart, was 1,647. Furthermore, based on the area ratios calculated from the gel osmosis chromatography (GPC) chart, the content of ester compound (A) in polyester resin (3) is 32%, and the content of ester compound (B) is 26%. The GPC chart of polyester resin (3) is shown in Figure 3.

(Examples 4-6 and Comparative Example 1)

<Preparation of Hardening Compounds>

Polyester resin, maleimide resin, and catalyst were mixed by heating according to the proportions shown in Table 1 to obtain a curable compound.

Maleimide resin: "BMI-5100" manufactured by Daiwa Chemical Industries, Ltd.

Catalyst: Diisopropylbenzene peroxide

<Production of Experimental Films>

The previously obtained curable composition was poured into a 2mm thick mold frame and heated at 200°C for 3 hours to harden. Subsequently, it was vacuum dried under heat and stored at 23°C and 50% humidity for 24 hours to obtain the test piece.

<Determination of Dielectric Loss Tangent>

According to Japanese Industrial Standards (JIS) C-6481, the dielectric loss tangent of the test piece at 1 GHz and 10 GHz was measured using an impedance material analyzer "HP4291B" manufactured by Agilent Technologies, Inc. Additionally, the dielectric loss tangent at 1 GHz and 10 GHz was measured after the test piece was placed under humid and hot conditions (121°C, 100% humidity) for 6 hours. The rate of change was also calculated. The results are shown in Table 1.

Claims (11)

A polyester resin comprising an ester compound (A) represented by the following general formula (1) and an ester compound (B) represented by the following general formula (2). In the general formula (1) ^{, Ar1} is an aryl group that may have substituents; ^Ar2 is an aryl group that may have substituents; ^R1 is an aliphatic hydrocarbon with 4 to 20 carbon atoms; and ^Ar1 in the general formula (1) has 1 to 3 alkenyl groups with 2 to 4 carbon atoms, alkynyl groups with 2 to 4 carbon atoms, alkenoxy groups with 2 to 4 carbon atoms, and alkynoxy groups with 2 to 4 carbon atoms, any one or more of these. In the general formula (2), ^Ar1 is an aryl group that can have substituents, and ^Ar2 is an aryl group that can have substituents. The polyester resin as described in claim 1, wherein the content of the ester compound (A) is in the range of 10% to 60%, calculated as a value based on the area ratio in a gel osmosis chromatography (GPC) chart. The polyester resin as described in claim 1, wherein the content of the ester compound (B), calculated based on the area ratio of gel osmosis chromatography (GPC), is in the range of 10% to 50%. A curing composition comprising a polyester resin as described in any one of claims 1 to 3. The hardening compound as described in claim 4 also contains a maleimide compound. A hardening agent, which is a hardened form of the hardening composition as described in claim 4. A prepreg using a curing composition as described in claim 4 or claim 5. A printed wiring board using a curable composition as described in claim 4 or claim 5. A laminated film using a curable composition as described in claim 4 or claim 5. A semiconductor sealing material using a hardening composition as described in claim 4 or claim 5. A semiconductor device using the semiconductor sealing material as described in claim 10.