JPH09328480A - Aryl ester compound and its production, and epoxy resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of giving curing products with both low dielectric constant and dissipation factor, useful as e.g. an epoxy resin curing agent, by esterifying the hydroxyl groups of a condensate from a specific resorcinol derivative and carbonyl compound. SOLUTION: First, a condensation reaction is carried out between a (substituted) resorcinol compound of formula I (P is H, a halogen, 1-10C alkyl, 5-10C cycloalkyl, 6-20C aryl or 7-20C aralkyl; (i) is an integer of 0-2) and a carbonyl compound of formula II (X and X' are each H, a 1-10C alkyl, 5-10C cycloalkyl, 6-10C aryl or 7-20C aralkyl, or may be combined with each other into a ring) to form a polyhydric phenol of formula III ((n) is 1-20; R1 to R5 are each the same kind of group as X). Subsequently, at least one OH group of the polyhydric phenol is esterified by an organic acid such as a 1-20C organic polyacid or derivative therefrom, thus obtaining the objective new aryl ester compound capable of giving cured products with both low dielectric constant and dissipation factor, and useful as e.g. an epoxy resin curing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aryl ester compound which can be mainly used as an epoxy resin curing agent and gives a cured product having a low dielectric constant and a low dielectric loss tangent, a method for producing the same, and an epoxy resin using the same. It relates to a composition.

[0002]

2. Description of the Related Art As a material for a printed wiring board among epoxy resins used for electric and electronic applications, a combination of a bisphenol type epoxy resin and dicyandiamide has been mainly used. In recent years, as the printed wiring board has become thinner and more multilayered, the resin has a low dielectric constant for the purpose of improving the signal speed and impedance matching of the circuit. Are required to have a low dielectric loss tangent. In contrast, a method has been devised in which a conventional epoxy resin is combined with a thermoplastic resin having a low dielectric constant and a low dielectric loss tangent. For example, a method of modifying with a reactive polybutadiene resin, a method of dispersing a powder of polytetrafluoroethylene resin, and the like. However, in these conventional techniques, the ratio of the thermoplastic resin to be combined increases in order to achieve the desired dielectric constant because the basic epoxy resin has a high dielectric constant,
The heat resistance, adhesiveness, dimensional stability, chemical resistance, etc., which are the characteristics of epoxy resin, are impaired.

[0003]

Therefore, an object of the present invention is to cure an epoxy resin so as to provide a cured product having a low dielectric constant and a low dielectric loss tangent without impairing the heat resistance, adhesiveness and workability of conventional epoxy resins. Compounds that can be used as agents and their manufacturing methods,
And to provide an epoxy resin composition thereof.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on the functional group structure and skeleton structure of a compound capable of undergoing a thermosetting reaction with an epoxy resin, and as a result, have found that a compound having a specific functional group structure and skeleton structure Found that the above object was satisfied, and completed the present invention. That is, the present invention provides the following general formula (1)

[0005]

Embedded image (In the formula, P is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyl group, i represents an integer value of 0 or more and 2 or less), and an unsubstituted or substituted resorcinol compound represented by the following general formula (2):

[0006]

Embedded image (In the formula, X and X'are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyl group, and X and X ′ may form a ring.) The OH group of the polyphenol, which is a condensation product with a carbonyl compound, has 1 carbon atom.
An aryl ester compound esterified with an organic acid having 1 to 20 carbon atoms or a derivative thereof, including an organic polyacid having 1 to 20 or a derivative thereof; a compound represented by the general formula (1); A product obtained by condensing the compound represented by (2) in the presence of an acid catalyst, in the presence of a base, containing an organic polyacid having 1 to 20 carbon atoms or a derivative thereof, having 1 to 1 carbon atoms. A method for producing an aryl ester compound esterified with an organic acid having 20 or a derivative thereof; (1) an epoxy resin, (2) the above aryl ester compound, and (3) an epoxy resin composition containing a curing accelerator as an essential component. And a cured product of the epoxy resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION More preferable polyhydric phenol as a raw material for the aryl ester compound of the present invention is the following general formula (3).

[0008]

[Chemical 6] (In the formula, n is the average number of repetitions and is 1 or more and 20 or less. P is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, i represents an integer of 0 to 2. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ Is
Each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or represents an aralkyl group having a carbon number of 7 to 20, R ₁ And R ₂ , and R ₄ and R ₅ may independently form a ring. ).

The equivalent ratio of the total organic acid used in the synthesis of the aryl ester to the polyphenol as a raw material is preferably 30% or more, more preferably 50% or more.
Of the organic acids having 1 to 20 carbon atoms or derivatives thereof used for esterification, the organic polyacid having 1 to 20 carbon atoms or its derivative is preferably 10% or more and 50% or less, and if less than this, epoxy resin The heat resistance of the cured product of the composition is lowered, and if it is more than this, a high molecular weight and further gelation occur during the synthesis of the aryl ester.

In the general formula (3), n represents the average number of repetitions and can take a value of 1 or more and 20 or less, but from the viewpoint of operability, it is preferably 1 or more and 10 or less. The polyhydric phenol compound as a raw material for the aryl ester compound of the present invention can be obtained by a known method such as a condensation reaction of resorcinols and a carbonyl compound in the presence of an acid. Here, as resorcinols, those not having a substituent at the 4- and 6-positions, resorcinol,
2-methylresorcinol, 5-methylresorcinol, 2-propylresorcinol, 2-n-butylresorcinol, 5-isobutylresorcinol, 5-t-
Butyl resorcinol, 5-octyl resorcinol,
Alkyl resorcinol typified by 5-nonylresorcinol, 2,5-dimethylresorcinol, 2,5-diethylresorcinol, 2,5-diisopropylresorcinol, 2-methyl-5-butylresorcinol, 2-methyl-5-nonylresorcinol and the like. Or a cycloalkylresorcinol represented by 2-cyclopentylresorcinol, 2-cyclohexylresorcinol, 2-cycloheptylcresol or the like, or arylresorcinol such as 5-phenylresorcinol or 5-naphthylresorcinol, or ,
Aralkyl resorcinols such as 5-benzylresorcinol, 5-phenethylresorcinol, 2-chlororesorcinol, 5-chlororesorcinol, 2,5-dichlororesorcinol, 2-bromoresorcinol, 5
Examples include halogenated resorcinols such as -bromoresorcinol, 2,5-dibromoresorcinol, 2-iodresorcinol, 5-iodresorcinol, and 2,5-diiodresorcinol. Examples of the carbonyl compound, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentyl aldehyde, phenylacetaldehyde, cyclohexylacetaldehyde and other aldehydes, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, Methyl cyclohexanone, cycloheptanone, benzyl phenyl ketone, benzyl methyl ketone, methyl phenethyl ketone, acetophenone, acetonaphthenone,
Examples include ketones such as indan-1-one.

Examples of acid catalysts used in the condensation reaction of resorcinols with carbonyl compounds include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid, benzenesulfonic acid and methanesulfonic acid, acid clay, activated alumina. , Solid acids such as zeolite, and acidic ion exchange resins. The amount of these acid catalysts is 0.01 to 50% by weight, and more preferably 0.5 to 20% by weight, based on the total weight of resorcinols and carbonyl compounds charged as raw materials. In the condensation reaction, a known non-reactive organic solvent may be used, and examples thereof include toluene, xylene, dioxane, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, methanol and ethanol. Not limited to. The molar ratio of resorcinols to carbonyl compounds at the time of the condensation reaction is from 0.1 to 2.0, preferably from 0.3 to 1.5. Beyond this range,
There is a problem that excess resorcinol remains or the OH residue of the product decreases. The reaction temperature is 0 to 200.
The temperature is 20 ° C to 160 ° C, more preferably 20 to 160 ° C.
When the temperature exceeds this range, the addition rate decreases when the temperature is low, and a large amount of by-products are generated when the temperature is high. The reaction time is 1 to 100 hours, more preferably 2 to 80 hours. If it exceeds this range, the reaction is incomplete if the time is short, and the yield does not change even if the reaction is carried out for a longer time, which is not economical. At the time of the condensation reaction, water generated by the reaction may or may not be removed from the system. In the case of removal, the reaction may be carried out using an apparatus such as a Dean-Stark tube capable of performing a reaction while removing water in the system using a solvent capable of azeotropic dehydration such as toluene and xylene. Further, the reaction may be performed under reduced pressure to promote dehydration.

The esterification of the condensation reaction product is carried out by reacting with an organic acid having 1 to 20 carbon atoms, an acid anhydride or an acid halide thereof in the presence of a base. Exemplifying the organic acid and its derivative, the organic polyacid and its derivative essential in the synthesis of the aryl ester of the present invention represent an organic compound having two or more carboxyl groups and its acid anhydride or acid halide, To illustrate, aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, fumaric acid, and citraconic acid, and their acid halides and acid anhydrides, phthalic acid, isophthalic acid, Aromatic polycarboxylic acids such as terephthalic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid and their acid halides and acid anhydrides, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid and other alicyclic polycarboxylic acids and Those acid halides and acids And the like anhydride, but is not limited thereto.

Organic acids and their derivatives which can be used in the synthesis of the aryl ester of the present invention include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid,
Aliphatic monocarboxylic acids such as stearic acid, phenylacetic acid, bromoacetic acid and their acid halides and acid anhydrides, benzoic acid, methylbenzoic acid, naphthoic acid, aromatic monocarboxylic acids such as biphenylcarboxylic acid and their acids Halides and acid anhydrides, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloaliphatic monocarboxylic acids such as cycloheptanecarboxylic acid and their acid halides and acid anhydrides, and the like,
It is not limited to these. Examples of the basic compound used in the esterification reaction include inorganic base compounds such as sodium hydroxide and potassium hydroxide, and organic base compounds such as pyridine, triethylamine, triphenylphosphine and imidazole compounds. In the esterification reaction, a known organic solvent may be used, and toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dioxane, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. Although exemplified, toluene, xylene and methyl isobutyl ketone are preferred. The molar equivalent ratio of all the organic acids or derivatives thereof used in the esterification reaction to the OH groups of the polyhydric phenol is 0.3 to 2.0, more preferably 0.5 to 1.5. If it exceeds this range, there is a problem that an excessive amount of the organic acid remains or the acylation rate of the product decreases. The reaction is carried out at a temperature of from 20 to 200 ° C., preferably from 40 to 150 ° C. When the temperature exceeds this range, the addition rate decreases when the temperature is low, and a large amount of by-products are generated when the temperature is high. Reaction time is 2-5
It is 0 hours, more preferably 4 to 30 hours. Above this range, if the time is short, the reaction will be incomplete,
It is not economical because the yield does not change even if it is carried out for a longer time. When the organic acid itself is used as a raw material in the ester reaction, water generated by the reaction may or may not be removed from the system. In the case of removal, the reaction may be carried out using a solvent such as toluene, xylene, methyl isobutyl ketone or the like which can be reacted while removing water in the system using an azeotropic dehydration solvent such as toluene, xylene and methyl isobutyl ketone. Further, the reaction may be performed under reduced pressure to promote dehydration.

The epoxy resin used in the present invention is a known compound containing two or more epoxy groups in the molecule, and its chemical structure is not particularly limited. For example, a bifunctional epoxy such as diglycidyl ether of bisphenol A, diglycidyl ether of tetrabromobisphenol A, or glycidyl ether of tris (4-hydroxyphenyl) methane, 1,
Trifunctional epoxy such as glycidyl ether of 1,1-tris (4-hydroxyphenyl) ethane, or glycidyl ether of phenol novolac, glycidyl ether of cresol novolak, and dehydration condensation of phenols with hydroxyaryl aldehydes Novolak glycidyl ether, poly (4
-Hydroxystyrene) glycidyl ether, phenol-modified polybutadiene glycidyl ether, phenol-dicyclopentadiene adduct glycidyl ether, bisphenol A novolac glycidyl ether polyfunctional epoxy, epoxy resin and bisphenol A, resorcinol, tetrabromo Examples of the product include a product obtained by previously reacting a phenol compound such as bisphenol A or tetrachlorobisphenol A, and a mixture of two or more kinds of epoxy resins. Is more preferably an epoxy resin having at least one alkyl group having 4 or more carbon atoms in one molecule in the aromatic nucleus as a substituent. For example, 2-t-butyl-5-methylphenol novolak glycidyl. Ether, glycidyl ether of cyclohexylphenol novolak, glycidyl ether of octylphenol novolak, 1,1 (4-hydroxy -5-t-butyl-2-methylphenyl) diglycidyl ether of butane, Rimonenbisu (2-sec
-Butylphenol) diglycidyl ether and the like.

Further, the quantitative ratio of the epoxy resin to the aryl ester compound in the present invention is such that the ratio of the number of moles of epoxy groups in the epoxy resin to the number of moles of ester groups in the aryl ester compound is 1: 0.3 to. It is preferable to mix them in a ratio of 1: 1.5, more preferably 1
The range is 0.5 to 1 to 1.2. If it is out of this range, curing failure will occur and a good cured product cannot be obtained. The curing accelerator in the present invention is a usual compound that accelerates the curing reaction between the epoxy resin and the curing agent, and examples thereof include 2-ethyl-4-methylimidazole, imidazoles such as 4-methylimidazole, triethylamine, and the like.
Benzyldimethylamine, 1,4-diazabicyclo [2.2.2]
Examples include tertiary amines such as undecene, quaternary ammonium salts such as tetra n-butyl ammonium bromide and tetra n-amyl ammonium bromide, and phosphorus compounds such as triphenylphosphine. Further, it is desirable to add such a quantitative ratio so as to be 0.05 to 3% by weight in the whole resin. Further, to the extent that the effects of the present invention are not impaired,
It is also possible to use a thermosetting resin other than the epoxy resin or a thermoplastic resin having a functional group in combination. Specific examples include a cyanate resin, a maleimide resin, glycidyl-modified polybutadiene, and maleic anhydride-modified polyethylene. Known additives such as flame retardants and surface treatment agents may be added to the epoxy resin composition of the present invention depending on the purpose. Examples of the flame retardant include antimony trioxide, aluminum hydroxide, red phosphorus and the like, and examples of the surface treatment agent include a silane coupling agent. The aryl ester compound of the present invention is used as a curing agent for epoxy resins. Further, the epoxy resin composition of the present invention is particularly suitable for high frequency electric and electronic applications, for example, resin for laminates and resin for IC encapsulation, but molding materials, coating materials, adhesive materials,
Also used for civil engineering and construction materials.

[0016]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In the examples, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group, and the OH equivalent is defined by the molecular weight of the polyphenol compound per OH group. Synthesis Example 1 This synthesis example relates to a process for producing a glycidyl ether of 2-t-butyl-5-methylphenol novolak, which is a raw material of the epoxy resin used in the epoxy resin composition of the present invention. 2-t-butyl-5-methylphenol 2231.0g (13.58 OHmol eq.), P-toluenesulfonic acid 12.9g (0.068mol), ion-exchanged water 223.2g thermometer,
A 5-liter 4-neck round bottom flask equipped with a stirrer, a cooling tube, and a dropping tube is charged, and the temperature is raised to 100 ° C. 218.4 g (2.715 mol) of 37% formalin was added dropwise over 2 hours, and then 100
The reaction was carried out by keeping the temperature at 2 ° C for 2 hours. Thereafter, the mixture was cooled to 80 ° C. and neutralized with 27.7 g (0.069 mol) of a 10% aqueous NaOH solution. The separated organic layer was washed twice with 700 g of ion-exchanged water. The organic layer after washing was concentrated under reduced pressure (180 ° C./10 mmHg / 1 hour) to obtain 857.2 g of a resinous material. The OH equivalent of the obtained resinous material is 17
It was 6.0 g / eq. Reaction product 2 obtained as described above
46.4 g (1.4 OHmol eq.), Epichlorohydrin 906.5 g (9.
8 mol), dimethyl sulfoxide 453.3 g, ion-exchanged water
14.0 g was charged into a 2 liter 4-neck round bottom flask equipped with a thermometer, a stirrer and a cooling tube with a separating tube, and the temperature was 49 ° C 42tor.
48.6% caustic soda aqueous solution 108.31g (1.316m
ol) is added dropwise over 5 hours. During this time, while maintaining the temperature at 49 ° C., azeotropic epichlorohydrin and water were cooled and liquefied, and the reaction was performed while returning the organic layer into the reaction system. After completion of the reaction, unreacted epichlorohydrin was removed by concentration under reduced pressure, an epoxidized product containing by-product salt and dimethyl sulfoxide was dissolved in methyl isobutyl ketone, and the by-product salt and dimethyl sulfoxide were removed by washing with warm water. By removing the solvent under reduced pressure, epoxy resin 304.9g
I got The epoxy equivalent of the epoxy resin thus obtained was 256 g / eq. As a result of infrared absorption spectrum measurement, absorption of phenolic OH 3200-3600 cm ^-1 disappeared,
It was confirmed that the epoxide had an absorption of 1240 and an absorption of 910 cm ^-1 .

Synthetic Example 2 In this Synthetic Example, the epoxy resin obtained in Synthetic Example 1, a diglycidyl ether of tetrabromobisphenol A, and an addition reaction of tetrabromobisphenol A were used.
The present invention relates to a method for obtaining a terminal epoxy resin. 83.8 g of the epoxy resin obtained in Synthesis Example 5, diglycidyl ether of tetrabromobisphenol A (Sumitomo Chemical Co., Ltd., trade name Sumiepoxy ESB-400, epoxy equivalent 403 g / eq) 75.5 g, tetrabromobisphenol A 1
7.5 g and 15.9 g of methyl ethyl ketone were charged into a 300 ml four-neck round bottom flask equipped with a thermometer, a condenser and a stirrer, and heated and melted at 110 ° C. Then, 0.71 g of a 10% solution of triphenylphosphine in methyl ethyl ketone
(The weight ratio of triphenylphosphine to the resin was 4 × 10 −4) was added, and the mixture was kept at 110 ° C. for 4 hours to carry out the addition reaction of the epoxy group and the phenolic hydroxyl group. After the reaction, the system was cooled to 90 ° C., and 63.5 g of propylene glycol monomethyl ether was added dropwise to obtain 250 g of a resin solution having a resin solid content of 70 wt%. The epoxy equivalent of the obtained resin adduct was 390.0 g / eq. In terms of solid content.

Synthesis Example 3 This synthesis example is a polyhydric phenol, 2,4,4-trimethyl-2-, which is a raw material of the aryl ester compound of the present invention.
The present invention relates to a method for producing (2,4-dihydroxyphenyl) -7-hydroxychroman (CAS No. 26505-28-2). Resorcinol 1000.0g (9.1 mol), p-toluenesulfonic acid 6.9g (0.036 mol), methanol 330.0g, acetone 176.0g (3.0 mol) thermometer, stirrer, cooling tube,
A 5-liter 4-neck round bottom flask equipped with a dropping funnel was charged and the temperature was raised to 65 ° C. After maintaining at 65 ° C. for 9 hours, 750 g of ion-exchanged water was charged, and after maintaining at 40 ° C. for 3 hours, precipitated crystals were filtered and washed. The obtained crude crystals were recrystallized by dissolving them in methanol and then adding ion-exchanged water dropwise. The yield after filtration and drying under reduced pressure was 265 g. 1H-NM
The product was confirmed to be the target by R and IR.

Example 1 This example relates to a method for producing the aryl ester of the present invention. The 2L four-necked flask equipped with a cooling tube, a thermometer, a stirrer, and a dropping device was charged with 2,2 obtained in Synthesis Example 3.
4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman 70 g (0.7 moleq.),
Triethylamine 77.8 g (0.77 moleq.), MIBK 300.8 g
, And raise the temperature to 70 ° C. Terephthalic acid dichloride 2
After a slurry solution prepared by dissolving 1.3 g (0.21 mole q.) In MIBK 168.0 g was added dropwise over 30 minutes, acetic anhydride 57.1 g (0.56 mole)
q.) is added dropwise over 1 hour. After raising the temperature to 90 ° C. and keeping it for 5 hours, it was washed with water to remove salts, and the solvent was removed under reduced pressure to obtain 96.9 g of a resinous solid. Infrared absorption spectrum: 2970, 1760 (carbonyl stretch of acetate), 1740 (carbonyl stretch of terephthalate), 1605, 1580, 1490, 1410, 1365, 1240, 120
0, 1145, 1120, 1100, 1070, 1055, 1010, 900, 720 cm
Absorption by ^-1 OH stretching vibration was not observed.

Example 2 This example relates to a process for preparing the aryl ester of the present invention. The 2L four-necked flask equipped with a cooling tube, a thermometer, a stirrer, and a dropping device was charged with 2,2 obtained in Synthesis Example 3.
4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman 70 g (0.7 moleq.),
Triethylamine 77.8 g (0.77 moleq.), MIBK 189.0 g
, And raise the temperature to 70 ° C. Isophthalic acid dichloride 2
After adding a slurry solution prepared by dissolving 1.3 g (0.21 mole q.) In MIBK 190.0 g in 30 minutes, acetic anhydride 57.1 g (0.56 mole)
q.) is added dropwise over 1 hour. After elevating the temperature to 90 ° C. and keeping the temperature for 5 hours, it was washed with water to remove salts, and the solvent was removed under reduced pressure to obtain 73.2 g of a resinous solid. Infrared absorption spectrum: 2970, 1765 (carbonyl stretching of acetate ester), 1740 (shoulder) (carbonyl stretching of isophthalic ester), 1610, 1585, 1495, 1420, 1375,
1300, 1210, 1145, 1125, 1055, 1015, 900, 755 cm ^-1 OH Stretching vibration absorption was not observed.

Examples 3 to 6 Glycidyl ether of o-cresol novolac as an epoxy resin (Sumitepoxy ES, trade name of Sumitomo Chemical Co., Ltd.)
CN-195, epoxy equivalent 195 g / eq), using the epoxy resin obtained in Synthesis Example 2, these and the compounds obtained in Examples 1 and 2, and 2-ethyl-4-methylimidazole (a curing accelerator). Shikoku Chemicals Co., Ltd. product name Curesol 2E
4MZ) at a ratio shown in Table 1 and dissolved in a solvent to form a uniform resin varnish. A resin mixture obtained by heating and distilling off the solvent from the resin varnish was press-molded to obtain a cured resin plate having a constant thickness. For the dielectric constant and dielectric loss tangent of the resin cured plate at 1 GHz, a cured sample with both sides polished was used as an impedance analyzer HP4291A manufactured by Hewlett-Packard Japan.
And the dielectric measurement electrode HP 16453A. The composition and the results are shown in Table 1.

Comparative Examples 1 to 4 Diglycidyl ether of bisphenol A as an epoxy resin (Sumiepoxy E, trade name, manufactured by Sumitomo Chemical Co., Ltd.)
LA-128) or a terminal epoxy resin obtained by addition reaction of diglycidyl ether of bisphenol A and tetrabromobisphenol A (Sumitomo Chemical Co., Ltd.)
Manufactured by Sumiepoxy ESB-500), phenol novolac resin (Tamanor 758, Arakawa Chemical Industry Co., Ltd.) or dicyandiamide as a curing agent, and 2-ethyl-4-methylimidazole (Cureazole 2E4MZ) was used to prepare a resin cured plate in the same manner as in Examples 3 to 6, and the dielectric constant and dielectric loss tangent at 1 GHz were measured.
The composition and the results are shown in Table 1.

[0023]

[Table 1]

INDUSTRIAL APPLICABILITY The aryl ester compound of the present invention has a lower dielectric constant than conventional ones as a curing agent for epoxy resins,
It gives a cured product with a low dielectric loss tangent. An epoxy resin composition using this gives a cured product with a low dielectric constant and a low dielectric loss tangent without impairing the heat resistance, adhesiveness, and processability of conventional epoxy resins, especially for high-speed arithmetic processing or high-frequency communication. Suitable for resins for multilayer printed wiring boards.

Claims (6)

[Claims] 1. The following general formula (1): (In the formula, P is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyl group, i represents an integer value of 0 or more and 2 or less), and an unsubstituted or substituted resorcinol compound represented by the following general formula (2): (In the formula, X and X'are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 7 carbon atoms. 20 represents an aralkyl group, and X and X ′ may form a ring.) At least one OH group of the polyhydric phenol, which is a condensation product with a carbonyl compound represented by An aryl ester compound esterified with an organic acid having 1 to 20 carbon atoms or a derivative thereof, including an organic polyacid having a number 1 to 20 or a derivative thereof. 2. A polyhydric phenol is represented by the following general formula (3): (In the formula, n is the average number of repetitions and is 1 or more and 20 or less. P is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms. Represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, i represents an integer of 0 to 2. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ Is
Each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or represents an aralkyl group having a carbon number of 7 to 20, R ₁ And R ₂ , and R ₄ and R ₅ may independently form a ring. ] The aryl ester compound of Claim 1 which is a compound represented by these. 3. The ratio of the organic polyacid having 1 to 20 carbon atoms or its derivative among the organic acids having 1 to 20 carbon atoms or its derivative used for esterification is in the range of 10% to 50%. The aryl ester compound according to claim 1 or 2. 4. A product obtained by condensing the compound represented by the general formula (1) according to claim 1 and the compound represented by the general formula (2) in the presence of an acid catalyst. The esterification with an organic acid having 1 to 20 carbon atoms or a derivative thereof including an organic polyacid having 1 to 20 carbon atoms or a derivative thereof in the presence of a base. A method for producing an aryl ester compound. 5. (1) Epoxy resin, and (2) claim 1,
An aryl ester compound according to 2 or 3, and (3)
An epoxy resin composition containing a curing accelerator as an essential component. 6. A cured product of the epoxy resin composition according to claim 5.