Ester-modified phenolic compounds

Abstract

To provide an ester modified phenolic compound that can give a cured product excelling in electric characteristics, heat resistance, crack resistance, moisture resistance, moldability and the like.SOLUTION: A ester modified phenolic compound comprises a phenolic compound represented by the formula (1) with a phenolic hydroxy group being wholly or partly esterified. In the formula 1, R's independently represent a hydrogen atom or a C1-6 hydrocarbon group, a is an integer of 0-4, b is an integer of 0-3 and n is an integer of 0-20.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention provides a method for producing a cured product having excellent electrical properties, heat resistance, etc., by reacting with an epoxy compound and a curing agent. The present invention relates to an ester-modified phenolic compound. [Background technology]

[0002] The cured product obtained by reacting an ester-modified phenolic compound with an epoxy resin or a curing agent has excellent electrical properties. Because of its excellent properties such as toughness and heat resistance, it is used in circuit boards, semiconductor encapsulation materials, machine parts, adhesives, etc. It is being done. For example, Patent Document 1 discloses a method for producing an ester of a phenol compound having a dicyclopentadiene skeleton. The cured product of the ester-modified phenolic compound is described as a multilayer printed circuit board insulating material. It is stated that it will be used as a fee. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2009-235165 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, the increasing density of semiconductors has led to increased heat generation during use, and the need to reduce the power consumption of high-frequency circuit board materials has become a problem. For this reason, electronic device components are required to have heat resistance, a low dielectric constant, a low dielectric tangent, and the like. However, the cured product of the ester-modified phenol compound described in Patent Document 1 has poor electrical properties. It wasn't enough. The present invention provides a cured product having excellent electrical properties, heat resistance, crack resistance, moisture resistance, moldability, etc. The present invention aims to provide an ester-modified phenolic compound which can be used in the manufacture of a phenolic compound having a molecular weight of 100 or more. [Means for solving the problem]

[0005] The gist of the present invention is to provide a phenolic compound represented by the following formula (1), The ester-modified phenol compound is obtained by esterifying a part or all of the phenol.

[0006] [ka]

[0007] In formula 1, each R is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. is an integer from 0 to 4, and b is an integer from 0 to 3. n is an integer from 0 to 20. Effect of the Invention

[0008] The ester-modified phenol compound of the present invention has excellent electrical properties, heat resistance, crack resistance, The cured product has excellent moisture resistance, moldability, etc. The cured product is useful for circuit boards, semiconductor encapsulation materials, Used for machine parts, adhesives, paints, civil engineering and building materials, insulating materials for electrical and electronic parts, optical materials, etc. Can be used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The ester-modified phenol compound of the present invention is a phenol compound represented by the following formula 1: It has a structure in which all or a part of the phenolic hydroxyl groups are esterified.

[0010] [ka]

[0011] The ester-modified phenolic compound of the present invention is derived from tricyclopentadiene (TCPD). This structure improves the heat resistance of the cured product. In addition, compared to conventional phenolic compounds, the hydroxyl group concentration is low and the polarity is low, The cured product has a low dielectric constant and low dielectric tangent. In the formula 1, each R is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. .

[0012] The hydrocarbon group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, Phenyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl In terms of flowability and curability, R is preferably a methyl group. Of these, an ethyl group is preferred, and a methyl group is more preferred. The bonding position (substitution position) of the R to the hydroxyl group of the benzene ring is set to be 100% because of the ease of production. The ortho or para position is preferred, and the para position is more preferred.

[0013] a is an integer of 0 to 4. In terms of fluidity, a is preferably an integer of 0 to 2, and more preferably an integer of 0 to 1. It is particularly preferable that the number is 0. b is an integer of 0 to 3. From the viewpoint of fluidity, b is preferably an integer of 0 to 2, and more preferably an integer of 0 to 1. It is particularly preferable that the number is 0. n is an integer of 0 to 20. From the viewpoints of fluidity and curing property, n is preferably an integer of 0 to 10, and more preferably 0. 1 to 5 is more preferable, and 0 to 2 is particularly preferable. Furthermore, in the present invention, the formula 1 is preferably a phenol compound represented by the following formula 2: It is nice.

[0014] [ka]

[0015] n is an integer of 0 to 20, preferably 0 to 10 from the viewpoints of fluidity and curing property, and 0 to 5 is more preferable, and 0 to 2 is particularly preferable. The compound which undergoes an esterification reaction with all or a part of the phenolic hydroxyl groups is , monocarboxylic acid or its acid halide, or dicarboxylic acid compound or its acid halide Examples include gen compounds.

[0016] The monocarboxylic acid or its acid halide has a high heat resistance and electrical resistance when cured. From the viewpoint of excellent characteristics, aromatic monocarboxylic acids or acid halides thereof are preferred. carboxylic acids, naphthalene carboxylic acids, and those having aliphatic hydrocarbon groups on the aromatic nucleus, alkoxy groups, Compounds having one or more substituents such as a silyl group, a halogen atom, an aryl group, or an aralkyl group, and Examples of the acid halide include acid halides of these.

[0017] The dicarboxylic acid compound or its acid halide has a high heat resistance when cured, From the viewpoint of excellent electrical properties, aromatic dicarboxylic acids or acid halides thereof are preferred. Phthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid Aromatic dicarboxylic acids such as carboxylic acid, 2,6-naphthalenedicarboxylic acid, and their acid fluorides Examples of the acid halide include acid chlorides, acid bromides, acid iodides, and the like.

[0018] Among these, acid halides of aromatic dicarboxylic acids are preferred because of their particularly good reactivity. isophthalic acid dichloride and terephthalic acid dichloride are more preferred. , and particularly preferred is the dichloride of isophthalic acid. In addition, when the ester-modified phenol compound of the present invention is used as a curing agent, the electrical conductivity of the cured product is increased. From the viewpoint of the gas properties, monocarboxylic acid or its acid halide, or dicarboxylic acid is used during esterification. Carboxylic acid compounds or their acid halides are used in combination with monohydroxy compounds, It is preferable that the aryl group has a structure derived from a monohydroxy compound.

[0019] The monohydroxy compound is preferred because it has excellent heat resistance and electrical properties when cured. Among these, aromatic monohydroxy compounds are preferred, and phenol, o-cresol, m-cresol, etc. p-cresol, 2,4-xylenol, 3,5-xylenol, o-phenylphenol Phenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol , 4-(1-methyl-1-phenylethyl)phenol, 1-naphthol, 2-naphthol Among these, 1-naphthol is particularly preferred because it reduces the dielectric tangent of the cured product. Preferred are 2-naphthol and 2-naphthol.

[0020] The phenolic compounds were analyzed by gel permeation chromatography (GPC) of standard polysaccharides. The number average molecular weight (Mn) in terms of styrene is preferably 400 to 1,000. The standard of the phenolic compounds was measured by gel permeation chromatography (GPC). The weight average molecular weight (Mw) in terms of polystyrene is preferably 450 to 1,500. The number average molecular weight and the weight average molecular weight are preferably high from the viewpoint of curability of the resin composition. From the viewpoint of suppressing gelation of the resin composition, a lower value is preferable. Furthermore, the hydroxyl group equivalent of the phenol compound can be determined by, for example, the amount of hydroxyl group in a pyridine-acetic anhydride solution. The hydroxyl equivalent of the cetylated product measured by alkali back titration is preferably 190 or more and 300 or less. The hydroxyl equivalent is preferably high from the viewpoint of the curability of the resin composition, and is preferably high to prevent gelation of the resin composition. From the viewpoint of inhibition, a lower value is preferable.

[0021] An example of a method for producing the phenol compound represented by the above formula 1 will be shown below. The phenol compound of the present invention is a phenol having a phenolic hydroxyl group, which is reacted with a phenolic acid in the presence of an acid catalyst. It can be produced by reacting alcohols with tricyclopentadiene. Tricyclopentadiene used as a raw material component of the phenolic resin of the present invention is, for example, Appl. Organometal. Chem. 2014, 28, P151-155 It can be synthesized from dicyclopentadiene by known methods such as the method described above.

[0022] The phenols are not particularly limited, but examples thereof include phenol, cresol, and chloroform. Silenol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol butylphenol, sec-butylphenol, tert-butylphenol, pentylphenol phenol, hexylphenol, and cyclohexylphenol. From the viewpoints of economy and ease of production, olefins such as cresol and xylenol are preferred. More than one species may be used in combination.

[0023] The molar ratio of tricyclopentadiene to phenols used in the reaction should be adjusted appropriately. This makes it possible to adjust the molecular weight and melt viscosity of the target phenol compound within an appropriate range. The molar ratio of phenols to tricyclopentadiene is preferably in the range of 2 to 64, and more preferably 4 The molar ratio of phenols / tricyclopentadiene is preferably in the range of 32 to 32. The ratio is preferably high from the viewpoint of the melt viscosity of the phenol compound, and is preferably low from the viewpoint of the synthesis efficiency. preferable.

[0024] Acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, as well as formic acid, acetic acid, oxalic acid, triacid, and acetic acid. Organic acids such as fluoromethanesulfonic acid, p-toluenesulfonic acid, and Friedel- As a Kraft catalyst, boron trifluoride, boron trifluoride ether complex, boron trifluoride Boron trifluoride-phenol complex, boron trifluoride-water complex, boron trifluoride-alcohol complex, Examples of the boron chloride-amine complex include boron chloride-amine complexes, and mixtures of these can also be used. Among these, boron trifluoride-phenofluoride is particularly preferred due to its catalytic activity and ease of catalyst removal. Boron trifluoride ether complex, trifluoromethanesulfonic acid, p-toluene Among these, sulfonic acids are preferably used.

[0025] The amount of catalyst used is specifically limited in order to set the molecular weight and melt viscosity of the resin within an appropriate range. For example, the reaction of phenol with tricyclopentadiene using p-toluenesulfonic acid as a catalyst is not limited to the above reaction. When reacting with benzene, p-toluenesulfonic acid / (phenol + tricyclohexane) Pentadiene) = 0.1 to 5.0% by weight is preferable, and 0.5 to 3.0% by weight is more preferable. It is nice.

[0026] The reaction is usually carried out in a closed system with the inside of the reactor replaced with an inert gas such as nitrogen or argon. It is preferable to carry out the reaction in an open system while supplying an inert gas into the reactor. . The reaction temperature is usually 60 to 180° C., preferably 100 to 160° C., and more preferably 120 From the viewpoint of reactivity, a higher temperature is preferable. From the viewpoint of suppressing the decomposition of cyclopentadiene, a lower value is preferable.

[0027] In the present invention, a phenol is reacted with tricyclopentadiene in the presence of an acid catalyst. In the reaction, a solvent may be used. Considering the high temperature reaction, the solvent is, for example, toluene, o- Xylene, p-xylene, m-xylene, ethylene glycol monobutyl ether, etc. are preferred. I wish. Furthermore, the reaction is terminated by deactivating the catalyst. The means of deactivation is not particularly limited. However, the amount of ionic impurities such as boron and fluorine remaining in the final phenolic resin is It is preferable to use a method that keeps the concentration of the ion exchange radicals at 100 ppm or less. The agent may be an alkali metal, an alkaline earth metal or an oxide, hydroxide, carbonate, or the like. Inorganic bases such as salts, ammonium hydroxide, hydrotalcites, ammonia gas, etc. There can be.

[0028] After the reaction is completed, the reaction solution is filtered or separated to remove the inactivating agent, etc., to obtain a reaction solution that does not contain impurities. When filtering, add a solvent, raise the temperature of the filtered material, or By making the internal pressure under increased or reduced pressure, workability can be improved. After removing the deactivator, the reaction mixture is concentrated by distillation to remove unreacted phenols. The distillation can be carried out under normal pressure, elevated pressure, or reduced pressure.

[0029] Next, an example of the method for producing the ester-modified phenol compound of the present invention will be described. The ester-modified phenol compound of the present invention is prepared by reacting the ester-modified phenol compound with the ester-modified phenol compound in the presence of an organic solvent and an alkali catalyst. The phenol compound and the monocarboxylic acid or its acid halide, or the dicarboxylic acid It can be produced by reacting a monohydrocarbon compound or its acid halide. It is preferable to use an oxy compound in combination.

[0030] The phenol compound and the monohydroxy compound, and the dicarboxylic acid or its acid halogen The reaction ratio with the ester compound is determined so that the desired active ester compound can be obtained in high yield and the amount of by-products can be reduced. Since the amount of the hydroxyl group contained in the phenol compound and the monohydroxyl compound is suppressed, The dicarboxylic acid or its acid halide is 0.47 to 0.53 moles per mole of the total of the groups. A molar ratio is preferred.

[0031] The ratio of the phenol compound and the monohydroxy compound used in the reaction is determined based on the equivalent weight of the hydroxyl group. The ratio is preferably 1.0 to 10.0, more preferably 1.5 to 5.0, and particularly preferably 2.0 to 4.0. The hydroxyl equivalent ratio is preferably high from the viewpoints of heat resistance and electrical properties of the cured product. From the viewpoints of the solubility of the steryl-modified phenol compound in a solvent and the inhibition of gelation, a lower value is preferred. The alkaline catalyst may be sodium hydroxide, potassium hydroxide, triethylamine, pyridine, or the like. These may be used alone or in combination of two or more. It is also possible to use a mixture of two or more of the above. It is also possible to use it as a 3.0 to 30% aqueous solution. Among them, sodium hydroxide, potassium hydroxide, and 4-dimethylaminopyridine, which have high catalytic activity, are preferred. I wish.

[0032] In addition to the alkali catalyst, an acid scavenger may be used in this reaction. Lysine, triethylamine, etc. can be used. The organic solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, Ketone solvents such as xanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene Glycol monomethyl ether acetate, carbitol acetate and other acetate esters solvents, cellosolve, butyl carbitol and other carbitol solvents;

[0033] Aromatic hydrocarbon solvents such as toluene and xylene, chloroform, dichloromethane, Examples of such amides include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in combination of two or more. Among these, phenol compounds and From the viewpoint of uniformly dissolving dicarboxylic acids or their acid chlorides and monohydroxy compounds, Toluene, xylene, and chloroform are preferred.

[0034] The reaction temperature is preferably 20 to 100°C, more preferably 20 to 80°C. The temperature is preferably from 20 to 60°C. The reaction pressure is preferably normal pressure. The reaction time is preferably 0.5 to 10 hours. More preferably, it is .about.5 hours. After the reaction is complete, if an aqueous solution of an alkaline catalyst is used, the reaction solution is allowed to stand and separated. The layers are removed, and the remaining organic layer is repeatedly left to stand and separated until the aqueous layer after washing becomes nearly neutral. Furthermore, the desired resin can be obtained by removing the solvent from the organic layer by distillation concentration. .

[0035] The ester-modified phenolic compounds of the present invention were analyzed by gel permeation chromatography (GPC). The number average molecular weight (Mn) measured in terms of standard polystyrene is preferably 500 to 1500. stomach. The ester-modified phenolic compound of the present invention can be analyzed by gel permeation chromatography (GPC). The weight average molecular weight (Mw) measured by standard polystyrene conversion is 1000 to 3000. is preferred.

[0036] The number average molecular weight and weight average molecular weight are preferably high from the viewpoint of the heat resistance and electrical properties of the cured product. In view of the solubility of the ester-modified phenol compound in a solvent and the inhibition of gelation, a lower value is preferable. stomach. The resin composition containing the ester-modified phenol compound of the present invention and an epoxy resin has electrical properties. The resulting cured product has excellent properties such as excellent adhesion, heat resistance, crack resistance, moisture resistance, and moldability.

[0037] The epoxy resin may be a bisphenol A type epoxy resin, a bisphenol C type epoxy resin, or the like. Epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bis Phenol AD ​​type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy Resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenone Divalent phenols such as tetramethylbiphenol type epoxy resins and tetramethylbiphenol type epoxy resins Epoxy resin derived from.

[0038] Phenol novolac epoxy resin, cresol novolac epoxy resin, tris Phenolmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene Tadiene-phenol modified epoxy resin, phenol aralkyl epoxy resin, biphenyl Phenyl aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol a Ralalkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol Toluene-cresol co-condensed novolac epoxy resin.

[0039] Aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl Epoxy resins derived from trivalent or higher phenols, such as modified novolac epoxy resins , Tetrabromobisphenol A type epoxy resin, Brominated phenol novolac type epoxy Examples of the resin include alkoxy resin. The epoxy resin may contain a polymeric epoxy resin or a phenoxy resin. Examples of polymeric epoxy resins include 1256, YX8100BH30, and YX6954. BH30, YX6900BH45, YX7553BH30, YX7482BH30, YX 7200B35, YX7800BH40, YX7891T30 (all manufactured by Mitsubishi Chemical) ) etc.

[0040] The epoxy resin is preferably a bisphenol A epoxy resin from the viewpoints of flowability and heat resistance of the cured product. A-type epoxy resin, bisphenol C-type epoxy resin, tetramethylbiphenol-type epoxy resin epoxy resin, 4,4'-biphenol type epoxy resin, biphenyl aralkyl type epoxy resin Epoxy resin, phenol aralkyl type epoxy resin, dicyclopentadiene-phenol modified epoxy resin Epoxy resin, orthocresol novolac type epoxy resin, trisphenol methane type epoxy resin Epoxy resins are preferred.

[0041] These epoxy resins may be used in combination of two or more kinds. It may be modified with a ester compound or the like. As an epoxy resin, it exhibits sufficient heat resistance after reacting with an ester-modified phenolic compound. In order to achieve this, the epoxy equivalent is preferably 400 g / equivalent or less, and 350 g / equivalent or less. More preferably, the weight is less than 300 g / equivalent, and even more preferably, the weight is less than 300 g / equivalent. In order to ensure sufficient reactivity with the modified phenol compound, the epoxy equivalent of the epoxy resin is The amount is preferably 100 g / equivalent or more, more preferably 120 g / equivalent or more, and more preferably 150 g / equivalent or more. More preferably still, the amount is 100%.

[0042] Polystyrene standards for epoxy resins measured by gel permeation chromatography (GPC) The converted weight average molecular weight (Mw) is preferably in the range of 500 to 10,000. If the Mw is 500 or more, the dielectric properties and / or water absorption rate tend to be excellent. From the viewpoint of maintaining the properties of the epoxy resin more favorably, the Mw of the epoxy resin is more preferably 600 or more. 00 or more is more preferable, and 1000 or more is particularly preferable.

[0043] In addition, the resin viscosity and / or softening point are kept appropriate, and the handling properties are improved. From this viewpoint, the Mw of the epoxy resin is preferably 10,000 or less, and more preferably 8,000 or less. , 7000 or less is more preferable, and 6000 or less is particularly preferable. The resin composition of the present invention is a resin composition comprising the above-mentioned The functional group equivalent ratio of the ester bond site of the ester-modified phenol compound is 0.2 or more, 5. It is preferably 0 or less, more preferably 0.5 or more and 2.0 or less, and more preferably 0.7 or more and 1.5 or less. If the value is larger or smaller than this range, the curability of the resin composition decreases and In addition, the heat resistance of the cured product may decrease.

[0044] The resin composition may contain additives such as a curing accelerator and an inorganic filler. Curing accelerators include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, and Examples of the tertiary amines include tertiary amines and imidazoles. The above may be used in combination. Inorganic fillers include fused silica, crystalline silica, glass powder, alumina, silicon nitride, and talc. Examples of the calcium phosphate include aluminum hydroxide, calcium carbonate, and calcium sulfate. These may be used in combination of two or more kinds.

[0045] The cured product obtained by curing the resin composition of the present invention has excellent crack resistance, heat resistance, moisture resistance, moldability, etc. Excellent, circuit boards, semiconductor encapsulation materials, machine parts, adhesives, paints, civil engineering and building materials, electrical and electronic It can be used as insulating material for parts, optical material, etc. EXAMPLES

[0046] The present invention will be described below with reference to examples. The present invention was evaluated by the following methods. .

[0047] Number average molecular weight (Mn) and molecular weight of phenolic compounds and ester-modified phenolic compounds and weight average molecular weight (Mw) Measurement was performed using a Tosoh Corporation GPC "HLC-8220GPC" under the following measurement conditions: did. As standard polystyrene, TSK Standard Polystyrene:F- 450, F-128, F-20, F-4, F-2, A-2500, A-1000 A calibration curve was created, and the number average molecular weight and weight average molecular weight were measured in terms of polystyrene. Ta. Column: Tosoh Corporation "TSKGEL SuperHZM-N" x 3 Eluent: Tetrahydrofuran Flow rate: 0.35ml / min Detection: RI Temperature: 40℃ Sample concentration: 0.1% by weight Injection volume: 10μl

[0048] <Weight average molecular weight of epoxy compound> Using a Tosoh Corporation GPC "HLC-8320GPC", the following measurement conditions were used. As quasi-polystyrene, F-128, F-10, F-4, F-2, A-5000, A-2 A calibration curve was created using A-500 and A-300, and the weight average molecular weight was converted to a polystyrene equivalent value. and measured. Column: TSKGEL SuperHM-H+H5000+H4000 manufactured by Tosoh Corporation +H3000+H2000" Eluent: Tetrahydrofuran Flow rate: 0.5ml / min Detection: UV (wavelength 254 nm) Temperature: 40℃ Sample concentration: 0.1% by weight Injection volume: 10μl

[0049] <Hydroxyl equivalent> A method using an acetylation reagent in accordance with the neutralization titration method of JIS K0070-1992 The hydroxyl equivalent of the phenol compound was measured.

[0050] <Epoxy equivalent> The epoxy equivalent of epoxy compounds was measured in accordance with JIS K7236:2001. In the case of a solution, the value is expressed as a solid content equivalent.

[0051] <Glass transition temperature> The analysis was performed using a viscoelasticity measuring device "DMS6100" manufactured by Hitachi High-Technologies Corporation. The temperature was increased from 30°C to 280°C at 5°C / min at 1GHz, and the elastic modulus tanδ(E'' / The maximum value of E') was taken as the glass transition temperature.

[0052] <Dielectric properties> A network analyzer was used to measure cavity resonance in a test piece of cured epoxy resin. The dielectric properties (dielectric constant: Dk, dielectric constant) at the measurement frequencies (1 GHz and 10 GHz) were measured by the perturbation method. The contact point Df was measured. (The size of the test piece was 2 mm wide, 80 mm long, and 300 μm thick. ) In addition, the dielectric properties were calculated using dedicated measurement software provided by the cavity resonator manufacturer. Used. Equipment used: Network analyzer manufactured by Agilent Technologies E8361A, Cavity resonator: CP215 (1GHz), CP184 (10GHz) manufactured by Kanto Electronics Application Development Co., Ltd. Measurement environment: Temperature 23℃, relative humidity 50%RH

[0053] <Raw materials used> The raw materials used in the following examples and comparative examples are as follows. Tricyclopentadiene (TCPD): Applied Organometallics c Chemistry), 2014, Vol. 28, p. 152. The transition metal catalyst was Pd(dba)2, and the ligand was P(p-tolyl). 3 was used. Phenol: Nacalai Tesque, Inc. p-Toluenesulfonic acid monohydrate: Fujifilm Wako Pure Chemical Industries, Ltd. Chloroform: Kanto Chemical Co., Ltd. Isophthalic acid dichloride: manufactured by Tokyo Chemical Industry Co., Ltd. 1-Naphthol: Tokyo Chemical Industry Co., Ltd. Triethylamine: Tokyo Chemical Industry Co., Ltd. 4,4'-Dimethylaminopyridine: Fujifilm Wako Pure Chemical Industries, Ltd. Toluene: Fujifilm Wako Pure Chemical Industries, Ltd. Ethyl acetate: Fujifilm Wako Pure Chemical Industries, Ltd. Silica gel (60N (spherical, neutral) 63-210 μm): Kanto Chemical Co., Ltd. Hardener (product name "HPC-8000-65T"): manufactured by DIC Corporation Epoxy resin (product name "YX7891T30", Mn: 10000, Mw: 30000, Epoxy equivalent: 6000g / equivalent, resin content: 30% by mass: Mitsubishi Chemical Corporation

[0054] <Production Example 1 (Phenol Compound)> Add 212.7 g (2. 26 mol) and 14.0 g (0.07 mol) of TCPD were added and replaced with nitrogen gas. The internal temperature was raised to 90°C and the contents were dissolved by heating. Add an aqueous solution of 4.2 g of enesulfonic acid monohydrate in 4.2 mL of water and keep the internal temperature at 90- The mixture was slowly added dropwise while maintaining the temperature at 100°C.

[0055] After that, the internal temperature was raised to 140°C and the reaction was carried out for 3 hours. After the reaction was completed, the internal temperature was lowered to 90°C. The temperature was lowered, and 6.2 g of a 20% aqueous potassium hydroxide solution was added to deactivate the catalyst. The temperature was raised to 0°C, and unreacted phenol was distilled off under reduced pressure. The reaction solution was then cooled to 60°C. The mixture was diluted with chloroform and transferred to a separatory funnel. The chloroform solution was washed with 20% potassium hydroxide aqueous solution, and then the pH of the aqueous layer was adjusted to 7. The solvent was removed using an evaporator, and the phenol compound (TCPD The phenol compound thus obtained was chromatographed. The mixture was purified with silica gel (eluent: ethyl acetate / toluene = 1 / 18) to give 21 g of compound. The purified phenolic compound had an Mn of 467, an Mw of 486, and a hydroxyl equivalent of 20. It was 9g / eq.

[0056] <Production Example 2 (Ester-modified phenol compound)> In a four-neck flask equipped with a rotor, a thermometer, and a dropping funnel, add phenol synthesized in Preparation Example 1. Compound (TCPD / PHL novolac) 7.5g (number of moles of phenolic hydroxyl group: 35. 9mmol), isophthalic acid chloride 5.1g (24.9mmol), 1-naphthol 2 0.1g (14.4mmol) and 0.1g of 4,4'-dimethylaminopyridine were added and nitrogen The gas was replaced.

[0057] Next, 65 g of toluene was added under a nitrogen flow and dissolved with stirring. Then, 5.1 g (50.1 mmol) of triethylamine was placed in the dropping funnel and the flask was covered with ice. The solution was cooled in a water bath and slowly dripped while keeping the internal temperature at 10-20°C. After dripping, the ice bath was removed. The mixture was allowed to react at an internal temperature of 20 to 30° C. for 3 hours. After the reaction was completed, the reaction solution was transferred to a separatory funnel and washed with water until the pH of the aqueous layer reached 7. After removing the solvent using an evaporator, the ester-modified phenolic compound (TCPD / PHL Novo The Mn of the resulting ester-modified phenol compound was 87. 3. Mw was 1822, and the ester value calculated from the amount charged was 3.58 mmol / g. .

[0058] <Production Example 3 (Epoxy Resin)> As the epoxy resin, orthocresol novolac epoxy resin (epoxy equivalent: 1 97g / equivalent, Mn: 416, average number of epoxy groups per molecule: 2.1) 100 parts by weight, As an ester compound, benzoic acid-2-naphthyl (active equivalent: 248 g / equivalent) 44.5 parts by weight, 4,4'-dimethylaminopyridine, 0.0400 parts by weight, toluene, 16.1 The weight parts were placed in a reaction vessel equipped with a stirrer and reacted at 130°C for 6 hours under a nitrogen gas atmosphere. (The reactive molar ratio of epoxy groups to ester groups is 2.8). Thereafter, the mixture was diluted with 45.9 parts by weight of toluene to obtain a modified epoxy resin solution. The epoxy equivalent of the modified epoxy resin (solid content) is 441g / equivalent, and the weight average molecular weight is 2040 The resin content was 69.7%.

[0059] <Example 1> 4,4'-Dimethylaminopyridine was dissolved in toluene to a content of 5% by mass. Each compound and solution was weighed and mixed to obtain the solid content ratio shown in Table 1. A solution of a resin composition was obtained. The obtained epoxy resin composition solution was applied to a release PET film (silicone-treated polyethylene terephthalate). The coating was applied to a 300μm thick, 5cm wide applicator on a polyethylene terephthalate film. Dry at 100°C for 0.5 hours, 160°C for 1.5 hours, and then 200°C for 1.5 hours. A film of a cured epoxy resin was obtained. The obtained cured film was cut into test pieces of the size required for each evaluation, and The heat resistance and dielectric properties were evaluated, and the results are shown in Table 1.

[0060] <Comparative Example 1> The 4,4'-dimethylaminopyridine was dissolved in toluene to a content of 5% by mass. The compounds and the solutions were weighed and mixed to obtain the solid content ratios shown in Table 1, and epoxy resin was prepared. A solution of the oil composition was obtained. The obtained epoxy resin composition solution was applied to a release PET film (silicone-treated polyethylene terephthalate). The coating was applied to a 300μm thick, 5cm wide applicator on a polyethylene terephthalate film. Dry at 100°C for 0.5 hours, 160°C for 1.5 hours, and then 200°C for 1.5 hours. A film of a cured epoxy resin was obtained.

[0061] The heat resistance and dielectric properties were evaluated, and the results are shown in Table 1.

[0062] [Table 1]

[0063] From Table 1, the curing agent containing the dicyclopentadiene type diphenol structure of Comparative Example 1 was used. The cured product has a low glass transition temperature, insufficient heat resistance, a high dielectric constant and dielectric tangent, and poor electrical properties. Inferior in character.

Claims

1. All or a part of the phenolic hydroxyl groups of a phenol compound represented by the following formula (1) An ester-modified phenol compound obtained by esterifying the above. 【Chemistry 1】 In formula 1, each R is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. is an integer from 0 to 4, b is an integer from 0 to 3, and n is an integer from 0 to 20.

2. The ester-modified phenol compound according to claim 1 , wherein the formula 1 is represented by the following formula 2: 【Chemistry 2】 In formula 2, n is an integer from 0 to 20.

3. The phenolic hydroxyl groups are all or partly substituted with a dicarboxylic acid compound or its acid halide. The ester-modified phenol according to claim 1 or 2, which is esterified with a phenol compound. Compound.

4. Any one of claims 1 to 3, wherein the terminal has a structure derived from a monohydroxy compound. Item 1. The ester-modified phenol compound according to item 1.

5. The ester-modified phenol compound according to any one of claims 1 to 4 and an epoxy compound. A resin composition comprising an oxy resin.

6. The epoxy resin according to claim 5, wherein the epoxy resin has a glycidyl group with two or more functional groups. The resin composition described above.

7. The ester-modified phenol compound is mixed in an amount of 1 / 2 equivalent to the epoxy group of the epoxy resin in the resin composition. and the functional group equivalent ratio of the ester bond site is 0.7 or more and 1.5 or less with respect to the amount of the ester bond site. Or the resin composition according to claim 6.

8. A cured product obtained by curing the resin composition according to any one of claims 5 to 7.

9. An electric or electronic part comprising the cured product of claim 8.

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