TW201815877A - Epoxy resin and cured product thereof - Google Patents

Abstract

Provided are: an epoxy resin characterized by having an extremely low dielectric constant and dielectric loss tangent; a curable resin composition containing same; a cured product thereof; a printed wiring board; and a semiconductor sealing material. An epoxy resin, a curable resin composition containing same, a cured product thereof, a printed wiring board, and a semiconductor sealing material, said epoxy resin characterized by having, as required reaction raw materials thereof: (A) an esterified product of (a1) a phenolic hydroxyl group-containing compound and (a2) an aromatic dicarboxylic acid or an acid halide thereof; and (B) a bifunctional epoxy compound.

Description

   Epoxy resin and its hardened material   

The present invention relates to an epoxy resin having characteristics of excellent heat resistance and extremely low dielectric loss tangent, a curable resin composition containing the epoxy resin, a cured product thereof, a printed wiring board, and a semiconductor sealing material.

In the technical field of insulating materials used in semiconductors, multilayer printed boards, etc., as the operating temperature of various electronic components increases or the speed and frequency of signals increase, development of new resin materials that follow these market trends is being pursued . For example, as the operating temperature of electronic components increases, the development of resin materials with high heat resistance is underway. In addition, in order to reduce energy loss such as heat generation associated with high-speed signals and high-frequency signals, development of a resin material having a low dielectric loss tangent is underway.

As a resin material having a low dielectric loss tangent, a high weight average molecular weight (Mw) of 5,000 to 200,000 obtained by reacting an epoxy resin such as biphenol diglycidyl ether with an ester compound such as diethyloxybiphenyl is known. Molecular weight epoxy resin (see Patent Document 1 below). Compared with the conventional resin materials, the epoxy resin described in Patent Document 1 has a characteristic that the dielectric loss tangent is low, but it does not meet the recent market requirement level, and has a lower heat resistance.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-89165

Therefore, the problem to be solved by the present invention is to provide an epoxy resin having excellent heat resistance and extremely low dielectric loss tangent, a curable resin composition containing the epoxy resin, a cured product thereof, a printed wiring board, and a semiconductor sealing material.

The present inventors conducted diligent research in order to solve the above-mentioned problems, and found that the following epoxy resin has the characteristics of excellent heat resistance and extremely low dielectric loss tangent, and thus completed the present invention; the epoxy resin is based on a phenolic hydroxyl group An esterified product of the compound, an aromatic dicarboxylic acid or an acidic halide thereof, and a bifunctional epoxy compound are used as essential reaction materials.

That is, the present invention relates to an epoxy resin, which is characterized in that it is an esterified product (A) of a phenolic hydroxyl-containing compound (a1) and an aromatic dicarboxylic acid or an acid halide (a2) thereof. , And bifunctional epoxy compound (B) are used as essential reaction raw materials.

The present invention further relates to a curable resin composition containing the epoxy resin and a hardener.

The present invention further relates to a cured product of the above-mentioned curable resin composition.

The present invention further relates to a printed wiring board using the curable resin composition.

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

According to the present invention, it is possible to provide an epoxy resin having characteristics of excellent heat resistance and extremely low dielectric loss tangent, a curable resin composition containing the epoxy resin, a cured product thereof, a printed wiring board, and a semiconductor sealing material.

[Fig. 1] Fig. 1 is a GPC diagram of the epoxy resin (1) obtained in Example 1. [Fig.

[Fig. 2] Fig. 2 is a GPC diagram of the epoxy resin (2) obtained in Example 2. [Fig.

[Fig. 3] Fig. 3 is a GPC line diagram of the epoxy resin (3) obtained in Example 3. [Fig.

[Fig. 4] Fig. 4 is a GPC line diagram of the epoxy resin (4) obtained in Example 4. [Fig.

[Fig. 5] Fig. 5 is a GPC line diagram of the epoxy resin (5) obtained in Example 5. [Fig.

Hereinafter, the present invention will be described in detail.

The epoxy resin of the present invention is characterized by comprising an esterified product (A) of a phenolic hydroxyl-containing compound (a1) and an aromatic dibasic acid or an acidic halide (a2) thereof, and a bifunctional epoxy compound (B). As an essential reaction raw material.

The compound (a1) containing a phenolic hydroxyl group may be any compound as long as it is an aromatic compound having a hydroxyl group on an aromatic ring, and other specific structures are not particularly limited. In the present invention, the phenolic hydroxyl group-containing compound (a1) may be used singly or in combination of two or more kinds. Specific examples of the phenolic hydroxyl-containing compound (a1) include phenol, naphthol, anthracenol, and compounds having one or more substituents on their aromatic cores. Examples of the substituent on the aromatic nucleus include: aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl; methoxy, Alkoxy groups such as ethoxy, propoxy, and butoxy; halogen atoms such as fluorine, chlorine, and bromine; phenyl, naphthyl, anthracenyl, and the aromatic nuclei are substituted with the above-mentioned aliphatic hydrocarbon groups Or an aryl group such as an alkoxy group, a halogen atom, etc .; phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl, and the aromatic cores thereof are substituted with the above-mentioned aliphatic hydrocarbon group or alkoxy group, Aralkyl and the like such as a halogen atom.

Among these, in terms of an epoxy resin having a lower dielectric loss tangent, a naphthol compound is preferred, and 1-naphthol or 2-naphthol is particularly preferred.

The aromatic dicarboxylic acid or its acid halide (a2) has a specific structure as long as it is an aromatic compound capable of reacting with the phenolic hydroxyl group of the phenolic hydroxyl-containing compound (a1) to form an esterified product (A). It does not specifically limit, It can be any compound. Moreover, an aromatic dicarboxylic acid or its acid halide (a2) may be used individually by 1 type, and may use 2 or more types together. Specific examples of the aromatic dicarboxylic acid or its acid halide (a2) include, for example, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, and benzenetricarboxylic acids such as 1,2,4-benzenetricarboxylic acid. Carboxylic acids; naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, etc .; Acidic halides, and the aromatic nucleus in which the above-mentioned aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted. Examples of the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. These can be used individually or in combination of 2 or more types. Among these, in terms of an epoxy resin having a lower dielectric loss tangent, a benzene dicarboxylic acid such as isophthalic acid or terephthalic acid or an acid halide thereof is preferred.

The reaction of reacting the phenolic hydroxyl-containing compound (a1) with the aromatic dicarboxylic acid or its acid halide (a2) to obtain an ester (A) can be performed, for example, by the following method: In the presence of the catalyst, heat and stir at a temperature of about 40 to 65 ° C. The reaction can also be carried out in an organic solvent as necessary. After the reaction is completed, the reaction product may be purified by washing with water or reprecipitation if necessary.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These can be used individually or in combination of 2 or more types. It can also be used as an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide having a high catalytic activity is preferable.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetate solvents; carbitol solvents such as cellulose and butylcarbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidine Ketones, etc. These can be used individually or as a mixture of two or more solvents.

From the viewpoint of obtaining the above-mentioned target ester (A) in a high yield, the reaction ratio of the above-mentioned phenolic hydroxyl-containing compound (a1) to the above-mentioned aromatic dicarboxylic acid or its acid halide (a2) is preferably relative to The aromatic carboxylic acid or its acid halide (a2) has a total of 1 mol of carboxyl group or halogenated fluorenyl group, and the phenolic hydroxyl-containing compound (a1) has a ratio of 0.95 to 1.05 mol.

The above-mentioned bifunctional epoxy compound (B) is not particularly limited as long as it is a compound having two epoxy groups in its molecular structure, other specific structures, and the presence or absence of a functional group. Any compound may be used. Moreover, a bifunctional epoxy compound (B) may be used individually by 1 type, and may use 2 or more types together.

The epoxy group of the bifunctional epoxy compound (B) is an ethylene oxide structure represented by the following structural formula (1). Specific examples of the epoxy group include an epoxypropyl ether group or a cyclic group. Oxycyclohexyl and the like.

(In the formula, R represents a hydrogen atom or various hydrocarbon groups, etc., and a ring structure may be formed by a plurality of Rs.)

Specific examples of the compound having a glycidyl ether group in the molecular structure in the bifunctional epoxy compound (B) include, for example, propylene oxide etherates of various glycol compounds.

Examples of the diol compound include a diol compound represented by any one of the following structural formulae (2-1) to (2-17), a ring-opening polymer of a diol compound and a lactone compound thereof, Modified polyoxyalkylene (polyoxyalkylene).

[In the formulae (2-1) to (2-17), R ¹ is an aliphatic hydrocarbon group having 2 to 10 carbon atoms or a structural site having one or more alkoxy groups or halogen atoms on its carbon atom. R ² and R ³ are each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group. k is an integer of 1 to 4, l is an integer of 0 or 1 to 4, m is an integer of 0 or 1 to 6, p is an integer of 0 or 1 to 3, and q is an integer of 0 or 1 to 5. Ar ¹ represents an aryl group which may have a substituent, and Ar ² represents a monohydroxy aryl group which may also have a substituent. In formulas (2-13) and (2-14), x and y are bonded to each other and adjacent carbon atoms to form Structure or dinaphthofuran structure. In formula (2-17), Z is any one of a hydrocarbon group, an oxygen atom, and a carbonyl group]

The propylene oxide etherification of the above-mentioned diol compound can be performed, for example, by the following method: one or more of the above-mentioned diol compound and an excess of epihalohydrin in the presence of a basic catalyst in a range of 20 to Reaction at 120 ° C for 0.5-10 hours. When a bifunctional epoxy compound (B) is obtained by such a method, by-products such as a reaction product of the propylene oxide etherified product and the diol compound of the reaction raw material can be produced. In this case, the epoxy equivalent of the obtained bifunctional epoxy compound (B) is preferably within 2.0 times the theoretical value.

Specific examples of the compound having an epoxycyclohexyl group in its molecular structure among the above-mentioned bifunctional epoxy compounds (B) include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexyl Alkyl carboxylates and the like.

The epoxy resin of the present invention may further use other compounds as reaction raw materials in addition to the above-mentioned esterified product (A) and the above-mentioned bifunctional epoxy compound (B). Other compounds include, for example, a tri- or more-functional epoxy compound (B '), or for introducing an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group as the aromatic core of the obtained epoxy resin. The substituent-introducing agent (C) and the like. When using the above-mentioned trifunctional or more epoxy compound (B '), it is preferred to use the epoxy compound raw material within the range of 2.5 or less in order to obtain film-forming energy.

The reaction between the esterified product (A) and the bifunctional epoxy compound (B) can be performed, for example, by the following method, namely, in the presence of a suitable reaction catalyst, at a temperature of about 100 to 180 ° C. Heat and stir. The reaction can also be carried out in an organic solvent, if necessary. After the reaction is completed, the reaction product may be purified by washing with water or reprecipitation if necessary.

Examples of the reaction catalyst include phosphorus-based compounds, tertiary amines, imidazole compounds, pyridine compounds, metal salts of organic acids, Lewis acids, and amine complex salts. Among these, triphenylphosphine is preferable among phosphorus compounds, and 1,8-diazabicyclo- [5.4.0] -undecene is preferred among tertiary amines in terms of excellent catalyst performance. DBU), 2-ethyl-4-methylimidazole is preferred among imidazole compounds, and 4-dimethylaminopyridine is preferred among pyridine compounds.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetate solvents; carbitol solvents such as cellulose and butylcarbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidine Ketones, etc. These may be used individually, or may be used as a mixed solvent of 2 or more types.

The reaction ratio of the esterified product (A) to the bifunctional epoxy compound (B) is preferably 1 mole relative to the epoxy group of the epoxy compound (B), and is in the esterified product (A). The Mohr number of the ester structure portion is used within a range of 0.5 to 1.

The epoxy group equivalent of the epoxy resin of the present invention is preferably in the range of 5,000 to 100,000 g / equivalent, and more preferably 7,500 to 50,000 g / equivalent in terms of the dielectric loss tangent and lower fat epoxy resin. Range.

The weight average molecular weight (Mw) of the epoxy resin of the present invention is preferably in the range of 5,000 to 100,000, and more preferably, it is an epoxy resin capable of obtaining film formation energy and having a lower dielectric loss tangent. A range of 7,500 to 60,000, particularly preferably a range of 8,000 to 50,000. The molecular weight distribution (Mw / Mn) is preferably in the range of 1.5 to 20, and more preferably in the range of 2 to 12.

The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the epoxy resin of the present invention are values measured by GPC measured under the following conditions.

Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation,

Column: Protective Column "HXL-L" manufactured by Tosoh Co., Ltd.

+ "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 Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ℃

Development solvent: tetrahydrofuran

Flow rate: 1.0ml / min

Standard: According to the above-mentioned "GPC-8320" measurement manual, the following monodisperse polystyrene with a known molecular weight is used.

(Using polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-1000" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

"F-40" manufactured by Tosoh Corporation

"F-80" manufactured by Tosoh Corporation

"F-128" manufactured by Tosoh Corporation

Sample: a solution obtained by filtering a 1.0% by mass tetrahydrofuran solution in terms of resin solid content by a microfilter (50 μl)

As an example of a specific structure of the epoxy resin of the present invention, for example, naphthol is used as the phenolic hydroxyl-containing compound (a1), isophthalic acid chloride is used as the aromatic dicarboxylic acid, or When the acid halide (a2) and bisphenol A propylene oxide ether are used as the bifunctional epoxy compound (B), the theoretical structure is exemplified by the following structural formula (3). In addition, the following structural formula (3) is only an example of a specific structure of the epoxy resin of the present invention, and does not exclude the above-mentioned phenolic hydroxyl-containing compound (a1) and the above-mentioned aromatic dicarboxylic acid or its acid halide (a2) ) And other resin structures that can be formed by reacting the esterified product (A) with the above-mentioned bifunctional epoxy compound (B).

The epoxy resin of the present invention may be used by blending a curing agent or a curing accelerator to form a curable resin composition. The hardener is not particularly limited as long as it is a compound capable of reacting with the epoxy resin of the present invention, and various compounds can be used. Examples of the hardening agent may include, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetriamine, diaminodiphenylphosphonium, isophoronediamine, imidazole, BF ₃ -amine compounds such as amine complexes, guanidine derivatives; dicyandiamine, polyamine compounds such as polyamine resin synthesized from the dimer of linolenic acid and ethylenediamine; phthalic anhydride, 1,2,4-phthalic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and other anhydrides; phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenol novolac resin , Dicyclopentadiene-phenol addition molding resin, phenol aralkyl resin, naphthol aralkyl resin, triphenol methane type resin, tetraphenol ethane type resin, amine tris Modified phenol resins such as phenol resins; active ester resins; cyanate resins; bismaleimide resins; benzo Resin; styrene-maleic anhydride resin; allyl-containing resin represented by diallyl bisphenol or triallyl isocyanurate; polyphosphate or phosphate-carbonate copolymer Wait. These can be used individually or in combination of 2 or more types.

The curable resin composition of the present invention may be used in combination with an epoxy resin other than the epoxy resin described above. Examples of other epoxy resins include phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin, bisphenol novolac epoxy resin, and biphenol novolac ring Oxygen resin, bisphenol epoxy resin, biphenyl epoxy resin, triphenol methane epoxy resin, tetraphenol ethane epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, phenol Aralkyl-type epoxy resin, naphthol-aralkyl-type epoxy resin, and the like.

The blending ratio of the epoxy resin, the hardener, and the other epoxy resins of the present invention is not particularly limited, and can be appropriately adjusted according to the desired properties of the hardened material and the like. As an example of the blending, the ratio of the total of functional groups in the hardener to 0.7 to 1.5 mol is preferred to the total of 1 mol of epoxy groups in the curable resin composition.

The curable resin composition of the present invention may optionally contain various additives such as a hardening accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier.

Examples of the hardening accelerator include phosphorus-based compounds, tertiary amines, imidazole compounds, pyridine compounds, metal salts of organic acids, Lewis acids, and amine complex salts. Among them, triphenylphosphine is preferred among phosphorus-based compounds, and 1,8-diazabicyclo is preferred among tertiary amines in terms of excellent hardenability, heat resistance, electrical characteristics, and humidity resistance reliability. -[5.4.0] -undecene (DBU), 2-ethyl-4-methylimidazole is preferred among imidazole compounds, and 4-dimethylaminopyridine is preferred among pyridine compounds.

Examples of the flame retardant include red phosphorus, ammonium dihydrogen phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and other inorganic phosphorus compounds such as ammonium phosphate; phosphate compounds, phosphonic acid compounds, and phosphinic acid (phosphinic acid) compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10 -dihydro-9-oxa-10-phospha phenanthrene-10-oxide), 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-Dihydroxynaphthyl) cyclic organic phosphorus compounds such as 10H-9-oxa-10-phosphaphenanthrene-10-oxide, and reacted with compounds such as epoxy resin or phenol resin Derivatives such as organic phosphorus compounds; three Compound, cyanuric acid compound, isocyanuric acid compound, phenanthrene Iso-nitrogen flame retardants; polysiloxane flame retardants such as silicone oil, silicone rubber, and silicone resin; metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, Inorganic flame retardants such as low melting glass. When using such a flame retardant, it is preferable that it is the range of 0.1-20 mass% in a curable resin composition.

The said inorganic filler is blended, for example, when using the curable resin composition of this invention for a semiconductor sealing material use. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, from the viewpoint that more inorganic fillers can be blended, the aforementioned fused silica is preferred. The fused silica may be used in either a broken shape or a spherical shape. In order to increase the amount of the fused silica and to suppress an increase in the melt viscosity of the hardening composition, it is preferable to use a spherical shape. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably blended in a range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

When the curable resin composition of the present invention is used for a conductive paste or the like, a conductive filler such as silver powder or copper powder can be used.

As described in detail above, the epoxy resin of the present invention has characteristics of excellent heat resistance and extremely low dielectric loss tangent. In addition, its general requirements for resin materials such as solubility in general organic solvents, or hardening properties with various hardeners are also high enough, except for printed wiring boards, semiconductor sealing materials, and resist materials. In addition to electronic materials, it can also be widely used in coatings, adhesives, and molded products.

When the curable resin composition of the present invention is used for a printed wiring board application or a build-up adhesive film application, it is generally preferred to use an organic solvent in a diluted state. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methylcellulose, and ethyl diethylene glycol. Acid esters, propylene glycol monomethyl ether acetate, and the like. The type or blending amount of the organic solvent can be appropriately adjusted according to the use environment of the curable resin composition. For example, in the application of printed wiring boards, methyl ethyl ketone, acetone, dimethylformamide, and cyclohexanone are preferred. The polar solvent having an isoboiling point of 160 ° C. or lower is preferably used in such a proportion that the non-volatile content becomes 25 to 80% by mass. In the application of the build-up adhesive film, acetone, methyl ethyl ketone, cyclohexanone and other ketone solvents are preferably used; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbitol Acetate solvents such as acetate; carbitol solvents such as celluloid and butylcarbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N- Methylpyrrolidone and the like; it is preferably used at a ratio of 25 to 60% by mass of the nonvolatile matter.

In addition, a method for producing a printed wiring board using the curable resin composition of the present invention includes, for example, a method of impregnating a reinforcing substrate with a curable resin composition and curing it to obtain a prepreg, which is overlapped with a copper foil and Perform thermal compression bonding. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven cloth, polyaramide paper, polyaramide cloth, glass felt, glass roving cloth, and the like. The impregnation amount of the curable resin composition is not particularly limited, and it is usually preferably prepared so that the resin component in the prepreg becomes 20 to 60% by mass.

When the curable resin composition of the present invention is used for a semiconductor sealing material, it is generally preferable to blend an inorganic filler. The semiconductor sealing material can be prepared by mixing a blend with an extruder, a kneader, a roll, or the like. Examples of the method for forming a semiconductor package using the obtained semiconductor sealing material include, for example, forming the semiconductor sealing material using a mold, a transfer molding machine, an injection molding machine, and the like, and then heating the semiconductor sealing material at a temperature of 50 to 200 ° C for 2 to 10 A method of hours, by which a semiconductor device that is a molded article can be obtained.

[Example]

Next, the present invention will be specifically described with reference to examples and comparative examples. The descriptions of "part" and "%" in the examples are based on quality unless otherwise specified. The measurement conditions of GPC in this example are as follows.

GPC measurement conditions

Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation,

Column: Protective Column "HXL-L" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

+ TSK-GEL G2000HXL manufactured by Tosoh Corporation

+ "TSK-GE LG2000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC Workstation EcoSEC- WorkStation" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ℃

Development solvent: tetrahydrofuran

Flow rate: 1.0ml / min

Standard: According to the above-mentioned "GPC-8320" measurement manual, the following monodisperse polystyrene with a known molecular weight is used.

(Using polystyrene)

"A-500" manufactured by Tosoh Corporation

"A-1000" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

"F-40" manufactured by Tosoh Corporation

"F-80" manufactured by Tosoh Corporation

"F-128" manufactured by Tosoh Corporation

Sample: a solution obtained by filtering a 1.0% by mass tetrahydrofuran solution in terms of resin solid content by a microfilter (50 μl)

Example 1: Production of epoxy resin (1) solution

To a flask equipped with a thermometer, a dropping funnel, a condenser tube, a shunt tube, and a stirrer were added 202 parts by mass of m-xylylenedichloride and 1,250 parts by mass of toluene, and the reaction system was purged with nitrogen under reduced pressure to dissolve . Then, 288 parts by mass of 1-naphthol was added, and the inside of the reaction system was purged with nitrogen under reduced pressure to be dissolved. Next, 0.6 parts by mass of tetrabutylammonium bromide was added, and the inside of the reaction system was controlled to 60 ° C. or lower while 400 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropwise addition, the reaction was continued by directly stirring for 1 hour. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred for about 15 minutes for mixing. Thereafter, the mixture was left to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the water layer became 7, and thereafter, drying under reduced pressure was performed to obtain 395 parts by mass of the esterified product (A-1) represented by the following structural formula (a).

Add a bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC Corporation, epoxy group equivalent weight: 173 g / equivalent) to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a diverter tube, and a stirrer. 176 parts by mass, 209 parts by mass of the ester compound (A-1) obtained previously, and 165 parts by mass of cyclohexanone were dissolved in a reaction system under reduced pressure nitrogen. Then, 0.15 parts by mass of dimethylaminopyridine was added, and the temperature in the reaction system was raised to 150 ° C. while purging with nitrogen. After reacting at 150 ° C for 24 hours, 285 parts by mass of cyclohexanone and 450 parts by mass of methyl ethyl ketone were added and diluted to obtain 1220 parts by mass of the epoxy resin (1) solution. The epoxy group equivalent of the epoxy resin (1) was 19,450 g / equivalent, the weight average molecular weight (Mw) was 37,180, and the molecular weight distribution (Mw / Mn) was 9.3. The GPC line of the obtained epoxy resin (1) is shown in FIG. 1.

Example 2: Production of epoxy resin (2) solution

Add a dihydroxynaphthalene-type epoxy resin ("HP-4032D" manufactured by DIC Corporation, epoxy group equivalent weight 141 g / equivalent) to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer 72 parts by mass, 105 parts by mass of the ester compound (A-1) obtained previously, and 76 parts by mass of cyclohexanone were dissolved in a reaction system under reduced pressure nitrogen. Next, 0.07 parts by mass of dimethylaminopyridine was added, and the temperature in the reaction system was raised to 150 ° C. while purging with nitrogen. After reacting at 150 ° C. for 12 hours, 130 parts by mass of cyclohexanone and 206 parts by mass of methyl ethyl ketone were added and diluted to obtain 549 parts by mass of an epoxy resin (2) solution. The epoxy group equivalent of the epoxy resin (2) was 34,860 g / equivalent, the weight average molecular weight (Mw) was 23,940, and the molecular weight distribution (Mw / Mn) was 6.8. The GPC line of the obtained epoxy resin (2) is shown in FIG. 2.

Example 3: Production of epoxy resin (3) solution

66 parts by mass of an alicyclic epoxy resin ("CEL2021P" manufactured by Daicel Corporation, epoxy equivalent 130 g / equivalent) was added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a diverter tube, and a stirrer 105 parts by mass of the previously obtained ester (A-1) and 73 parts by mass of cyclohexanone were dissolved in a reaction system under reduced pressure nitrogen. Next, 0.07 parts by mass of dimethylaminopyridine was added, and the temperature in the reaction system was raised to 150 ° C. while purging with nitrogen. After reacting at 150 ° C for 12 hours, 126 parts by mass of cyclohexanone and 199 parts by mass of methyl ethyl ketone were added and diluted to obtain 532 parts by mass of an epoxy resin (3) solution. The epoxy resin equivalent (3) had an epoxy group equivalent weight of 8,210 g / equivalent, a weight average molecular weight (Mw) of 10,000, and a molecular weight distribution (Mw / Mn) of 5.7. The GPC line of the obtained epoxy resin (3) is shown in FIG. 3.

Example 4: Production of epoxy resin (4) solution

To a flask equipped with a thermometer, a dropping funnel, a condenser tube, a diverter tube, and a stirrer, add a formula represented by the following structural formula (b): 136 parts by mass of epoxy resin (epoxy equivalent 265 g / equivalent) based on type epoxy compound, 105 parts by mass of previously obtained ester (A-1), and 103 parts by mass of cyclohexanone were carried out in a reaction system Dissolve under reduced pressure nitrogen substitution. Next, 0.10 parts by mass of dimethylaminopyridine was added, and the temperature in the reaction system was raised to 150 ° C. while purging with nitrogen. After reacting at 150 ° C. for 12 hours, 178 parts by mass of cyclohexanone and 281 parts by mass of methyl ethyl ketone were added and diluted to obtain 750 parts by mass of an epoxy resin (4) solution. The epoxy group equivalent of the epoxy resin (4) was 8,520 g / equivalent, the weight average molecular weight (Mw) was 23,530, and the molecular weight distribution (Mw / Mn) was 8.3. The GPC line of the obtained epoxy resin (4) is shown in FIG. 4.

Example 5: Production of epoxy resin (5) solution

To a flask equipped with a thermometer, a dropping funnel, a condenser tube, a shunt tube, and a stirrer, an epoxy resin (epoxy equivalent 246 g) containing a fluorene type epoxy resin represented by the following structural formula (c) as a main component was added. / Equivalent) 127 parts by mass, 105 parts by mass of the previously obtained esterified product (A-1), and 99 parts by mass of cyclohexanone were dissolved in a reaction system under reduced pressure nitrogen. Next, 0.09 parts by mass of dimethylaminopyridine was added, and the temperature in the reaction system was raised to 150 ° C. while purging with nitrogen. After reacting at 150 ° C. for 12 hours, 171 parts by mass of cyclohexanone and 270 parts by mass of methyl ethyl ketone were added and diluted to obtain 738 parts by mass of an epoxy resin (5) solution. The epoxy resin (5) had an epoxy group equivalent weight of 13,270 g / equivalent, a weight average molecular weight (Mw) of 21,000, and a molecular weight distribution (Mw / Mn) of 5.8. The GPC line of the obtained epoxy resin (5) is shown in FIG. 5.

Comparative Production Example 1: Production of epoxy resin (1 ') solution

Add a bisphenol A epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent 188 g / equivalent) to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer. ) 97 parts by mass, 109 parts by mass of bisphenol A dibenzosulfide, and 88 parts by mass of cyclohexanone were dissolved in a reaction system under reduced pressure nitrogen. Next, 0.08 parts by mass of dimethylaminopyridine was added, and the temperature in the reaction system was raised to 150 ° C. while purging with nitrogen. After reacting at 150 ° C for 36 hours, 152 parts by mass of cyclohexanone and 240 parts by mass of methyl ethyl ketone were added and diluted to obtain 650 parts by mass of an epoxy resin (1 ') solution. The epoxy resin equivalent (1 ') had an epoxy group equivalent weight of 6,650 g / equivalent, a weight average molecular weight (Mw) of 7,380, and a molecular weight distribution (Mw / Mn) of 2.3.

Examples 6 to 10 and Comparative Example 1

Film production and evaluation

The epoxy resin solutions obtained in Examples 1 to 5 and Comparative Manufacturing Example 1 were applied to a separator (polysiloxane-treated polyethylene terephthalate membrane) using a device, and dried at 80 ° C for 10 minutes. Furthermore, it dried at 150 degreeC for 1 hour, and produced the epoxy resin film with a thickness of 70 micrometers. Those who can maintain the shape of the film are judged as A, and those who cannot maintain the shape of the film are judged as B.

Determination of heat resistance (DSC-Tg)

For the epoxy resin film produced by the above method, DSC822e manufactured by METTLER TOLEDO was used, and DSC-Tg was measured at 10 ° C / min.

Measurement of dielectric loss tangent

The obtained epoxy resin film was dried under heating and vacuum, and then stored in a room at 23 ° C. and 50% humidity for 24 hours. Then, according to JIS-C-6481, the dielectric loss tangent of the epoxy resin film at 1 GHz was measured using Impedance Material Analyzers "HP4291B" manufactured by Agilent Technology Co., Ltd.

Claims (7)

    An epoxy resin comprising an esterified product (A) of a phenolic hydroxyl-containing compound (a1), an aromatic dicarboxylic acid or an acid halide (a2) thereof, and a bifunctional epoxy compound (B) As an essential reaction raw material.         For example, the epoxy resin in the scope of patent application No. 1 has an epoxy equivalent range of 5,000 to 100,000 g / equivalent.         For example, the range of the weight average molecular weight (Mw) of the epoxy resin in the first patent application range is 5,000 ~ 100,000.         A curable resin composition containing an epoxy resin according to any one of claims 1 to 3 of the scope of patent application.         A hardened product is a hardened product of a hardenable resin composition according to item 4 of the patent application.         A printed wiring board is formed by using a curable resin composition according to claim 4 of the application.         A semiconductor sealing material is formed by using a hardenable resin composition according to item 4 of the patent application.