TWI726121B - Epoxy resin solution and manufacturing method thereof, and manufacturing method of epoxy resin film - Google Patents

Abstract

The present invention provides an epoxy resin with extremely low dielectric rate and dielectric loss tangent, a curable resin composition containing the epoxy resin, and a cured product thereof, a printed wiring board, and a semiconductor sealing material. The present invention is an epoxy resin, a curable resin composition containing the same, and a cured product thereof, a printed wiring board, and a semiconductor sealing material. The epoxy resin is characterized by using a phenolic hydroxyl-containing compound (a1) and an aromatic two The esterified compound (A) of carboxylic acid or its acid halide (a2) and the bifunctional epoxy compound (B) are necessary reaction materials.

Description

Epoxy resin solution and manufacturing method thereof, and manufacturing method of epoxy resin film

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

In the technical field of insulating materials used in semiconductors and multilayer printed circuit boards, as the operating temperature of various electronic components rises or the speed and frequency of signals increase, we are seeking to develop new resin materials that follow these market trends . For example, as the operating temperature of electronic components rises, resin materials with high heat resistance are being developed. In addition, in order to reduce energy loss such as heat generated by the increase in signal speed and frequency, the development of resin materials with low dielectric loss tangent is underway.

As a resin material with low dielectric loss tangent, it is known that an epoxy resin such as biphenol diglycidyl ether reacts with an ester compound such as diacetoxybiphenyl to obtain a high weight average molecular weight (Mw) of 5,000 to 200,000. Molecular weight epoxy resin (refer to Patent Document 1 below). Compared with the conventional resin materials, the epoxy resin described in Patent Document 1 has the characteristics of lower dielectric loss tangent, but it does not meet the recent market requirements and has lower heat resistance.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-89165 A

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, and a cured product thereof, a printed wiring board, and a semiconductor sealing material.

The inventors of the present invention made diligent studies 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, thereby completing the present invention; the epoxy resin series: containing phenolic hydroxyl groups The compound and the esterification of aromatic dicarboxylic acid or its acid halide, and bifunctional epoxy compound are required as raw materials for the reaction.

That is, the present invention relates to an epoxy resin characterized in that it is an ester compound (A) of a compound (a1) containing a phenolic hydroxyl group and an aromatic dicarboxylic acid or its acid halide (a2) , And bifunctional epoxy compound (B) as the necessary reaction materials.

The present invention further relates to a curable resin composition containing the above-mentioned epoxy resin and a curing agent.

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

The present invention further relates to a composition made of the above-mentioned curable resin composition Printed wiring board.

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

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

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

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

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

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

[Fig. 5] Fig. 5 is a GPC 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 the esterification (A) of a compound (a1) containing a phenolic hydroxyl group and an aromatic dicarboxylic acid or its acid halide (a2), and a bifunctional epoxy compound (B) As a necessary raw material for reaction.

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

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

The above-mentioned aromatic dicarboxylic acid or its acid halide (a2) is an aromatic compound that can react with the phenolic hydroxyl group of the above-mentioned phenolic hydroxyl group-containing compound (a1) to form an ester compound (A), the specific structure It is not particularly limited, and it may 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, benzene dicarboxylic acids such as isophthalic acid and terephthalic acid; and trimellitic acid such as trimellitic acid. Carboxylic acid; naphthalene dicarboxylic acid such as naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid; The acid halides, and these aromatic nuclei substituted with the above-mentioned aliphatic hydrocarbon groups or alkoxy groups, halogen atoms and other compounds. Examples of the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. These can be used individually or in combination Two or more kinds. Among them, in terms of becoming an epoxy resin with a lower dielectric loss tangent, phthalic dicarboxylic acids such as isophthalic acid or terephthalic acid or acid halides thereof are preferred.

The reaction of reacting the above-mentioned phenolic hydroxyl group-containing compound (a1) with the above-mentioned aromatic dicarboxylic acid or its acid halide (a2) to obtain the ester compound (A) can be carried out, for example, by the following method: In the presence of the catalyst, heating and stirring are carried out at a temperature of about 40~65℃. The reaction can also be carried out in an organic solvent as needed. Furthermore, after the reaction is completed, the reaction product may be purified by washing with water or reprecipitation as necessary.

Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These may be used individually, respectively, and may use 2 or more types together. In addition, it can also be used as an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide, which has a higher catalyst energy, is preferred.

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, carbitol acetate, etc. Acetate solvents; carbitol solvents such as celluloid and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidine Ketones and so on. These can be used alone, or can be made into a mixed solvent of two or more kinds.

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

The above-mentioned bifunctional epoxy compound (B) as long as it has two in the molecular structure For epoxy-based compounds, other specific structures or the presence or absence of functional groups are not particularly limited, and any compound can 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 contained in the bifunctional epoxy compound (B) is an oxirane structure represented by the following structural formula (1). Specific examples of the epoxy group include a glycidyl ether group or a ring Oxycyclohexyl and so on.

(In the formula, R represents a hydrogen atom or various hydrocarbon groups, etc., and multiple Rs may form a ring structure with each other)

As a specific example of the compound which has a glycidyl ether group in a molecular structure among the said bifunctional epoxy compound (B), the propylene dioxide etherification etc. of various diol compounds etc. are mentioned, for example.

The above-mentioned diol compound includes, for example, a diol compound represented by any one of the following structural formulas (2-1) to (2-17), or a ring-opening polymer of a diol compound such as a lactone compound, Polyoxyalkylene (polyoxyalkylene) modified products, etc.

[式(2-1)~(2-17)中，R¹為碳原子數2~10之脂肪族烴基或於其碳 原子上具有一個至多個烷氧基或鹵素原子的結構部位。R²、R³分別獨立地為脂肪族烴基、烷氧基、鹵素原子、芳基、芳烷基中之任一者。k為1~4之整數、l為0或1~4之整數、m為0或1~6之整數、p為0或1~3之整數、q為0或1~5之整數。Ar¹表示亦可具有取代基之芳基、Ar²表示亦可具有取代基之單羥基芳基。式(2-13)、(2-14)中，x與y互相和鄰接之碳原子鍵結，分別形成

結構或二萘并呋喃(dinaphthofuran)結構。式(2-17)中，Z為烴基、氧原子、羰基之任一者]

[In formulas (2-1) to (2-17), R ¹ is an aliphatic hydrocarbon group with 2 to 10 carbon atoms or a structural site having one to more alkoxy groups or halogen atoms on its carbon atoms. R ² and R ³ are each independently any one of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. k is an integer of 1 to 4, l is 0 or an integer of 1 to 4, m is 0 or an integer of 1 to 6, p is 0 or an integer of 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 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 (dinaphthofuran) structure. In formula (2-17), Z is any one of a hydrocarbon group, an oxygen atom, and a carbonyl group]

The etherification of propylene dioxide of the above-mentioned diol compound can be carried out, for example, by the following method, that is, one or more of the above-mentioned diol compound and an excess of epihalohydrin in the presence of a basic catalyst are used for 20~ React at a temperature of 120°C for 0.5-10 hours. When the bifunctional epoxy compound (B) is obtained by this method, by-products such as a reaction product of the produced propylene dioxide etherate 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.

As a specific example of the compound having an epoxycyclohexyl group in the molecular structure of the above-mentioned bifunctional epoxy compound (B), 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexyl can be cited Alkyl carboxylate and so on.

In addition to the above-mentioned esterified product (A) and the above-mentioned bifunctional epoxy compound (B), the epoxy resin of the present invention may further use other compounds as reaction raw materials. Examples of other compounds include epoxy compounds (B') with three or more functionalities, or they can be used to introduce aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, and aralkyl groups as the aromatic nucleus of the resulting epoxy resin. Substituent introduction agent (C) etc. In the case of using the above-mentioned epoxy compound (B') with three or more functionalities, in order to obtain the film formation performance, it is preferable that the average value of the epoxy compound raw material The number of functional groups is used within the range of 2.5 or less.

The reaction of the ester compound (A) and the bifunctional epoxy compound (B) can be carried out, for example, by the following method: 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 as needed. Furthermore, after the reaction is completed, the reaction product may be purified by washing with water or reprecipitation as necessary.

Examples of the aforementioned reaction catalyst include phosphorus-based compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, and amine complex salts. Among them, in terms of excellent catalyst performance, triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[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 organic solvent include: ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc. Acetate solvents; carbitol solvents such as celluloid and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidine Ketones and so on. These can be used individually, respectively, and can also be formed as a mixed solvent of 2 or more types.

The reaction ratio of the esterified compound (A) and the bifunctional epoxy compound (B) is preferably 1 mol relative to the epoxy group of the epoxy compound (B) in the esterified compound (A) The molar number of the ester structure part is used within the range of 0.5 to 1.

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

The weight average molecular weight (Mw) of the epoxy resin of the present invention can become In terms of obtaining an epoxy resin with film formation ability and lower dielectric loss tangent, the range of 5,000 to 100,000 is preferable, the range of 7,500 to 60,000 is more preferable, and the range of 8,000 to 50,000 is particularly preferable. In addition, the molecular weight distribution (Mw/Mn) is preferably in the range of 1.5-20, more preferably in the range of 2-12.

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

Measuring device: "HLC-8320GPC" manufactured by Tosoh Co., Ltd., column: protection column "HXL-L" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

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

Measurement conditions: column temperature 40℃

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

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

(Use polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

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

As an example of the specific structure of the epoxy resin of the present invention, for example, naphthol is used as the above-mentioned phenolic hydroxyl-containing compound (a1), isophthalic acid chloride is used as the above-mentioned aromatic dicarboxylic acid or When the acid halide (a2) and the propylene dioxide ether of bisphenol A are used as the bifunctional epoxy compound (B), the theoretical structure is exemplified in the following structural formula (3). Furthermore, the following structural formula (3) is only an example of the 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) Other resin structures that can be generated by the reaction of the esterified compound (A) of) and the above-mentioned bifunctional epoxy compound (B).

改質酚樹脂等酚樹脂；活性酯樹脂；氰酸酯樹脂；雙馬來亞醯胺樹脂；苯并

樹脂；苯乙烯-順丁烯二酸酐樹脂；以二烯丙基雙酚或異三聚氰酸三烯丙基酯為代表之含烯丙基樹脂；聚磷酸酯或磷酸酯-碳酸酯 共聚物等。該等可分別單獨使用，亦可併用2種以上。 The epoxy resin of the present invention can also be used by blending a curing agent or a curing accelerator to form a curable resin composition. The curing agent is not particularly limited as long as it is a compound that can react with the epoxy resin of the present invention, and various compounds can be used. As an example of the hardener, for example, it may also contain: diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, isophoronediamine, imidazole, BF ₃ -Amine compounds such as amine complexes and guanidine derivatives; dicyandiamine, polyamide resin synthesized from the dimer of hypolinoleic acid and ethylenediamine; phthalic anhydride, 1,2,4- trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, Acid anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride; 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, amino three

Modified phenol resins and other phenol resins; active ester resins; cyanate ester 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 may be used individually, respectively, and may use 2 or more types together.

The curable resin composition of the present invention may also use other epoxy resins in addition to the above-mentioned epoxy resins. Examples of other epoxy resins include: phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, bisphenol novolak type epoxy resin, and biphenol novolak type epoxy resin. Oxygen resin, bisphenol type epoxy resin, biphenyl type epoxy resin, triphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol Aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, etc.

The blending ratio of the epoxy resin of the present invention, the above-mentioned curing agent, and the above-mentioned other epoxy resins is not particularly limited, and can be appropriately adjusted according to the desired properties of the cured product and the like. As an example of blending, it is preferable that the total of the functional groups in the curing agent be 0.7 to 1.5 mol relative 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 curing accelerators, flame retardants, inorganic fillers, silane coupling agents, mold release agents, pigments, and emulsifiers.

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

化合物、三聚氰酸化合物、異三聚氰酸化合物、啡噻

等氮系阻燃劑；聚矽氧油、聚矽氧橡膠、聚矽氧樹脂等聚矽氧系阻燃劑；金屬氫氧化物、金屬氧化物、金屬碳酸鹽化合物、金屬粉、硼化合物、低熔點玻璃等無機阻燃劑等。於使用該等阻燃劑之情形時，較佳為於硬化性樹脂組成物中為0.1~20質量%之範圍。 Examples of the above-mentioned flame retardants include: red phosphorus, ammonium dihydrogen phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate and other ammonium phosphates, ammonium phosphate and other inorganic phosphorus compounds; phosphate ester compounds, phosphonic acid compounds, and phosphinic acid (phosphinic acid) compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 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-phospha phenanthrene-10-oxide, 10- (2,7-Dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organophosphorus compounds, and reacted with epoxy resin or phenol resin and other compounds Derivatives and other organic phosphorus compounds; three

Compounds, cyanuric acid compounds, isocyanuric acid compounds, phenanthrene

Nitrogen-based flame retardants; silicone oil, silicone rubber, silicone resin and other silicone-based flame retardants; metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, Inorganic flame retardants such as low melting point glass, etc. When these flame retardants are used, it is preferably in the range of 0.1 to 20% by mass in the curable resin composition.

The above-mentioned inorganic filler is blended, for example, when the curable resin composition of the present invention is used for semiconductor sealing materials. Examples of the above-mentioned inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, in terms of blending more inorganic fillers, the above-mentioned fused silica is preferred. The above-mentioned fused silica can be used in either crushed or spherical shapes. In order to increase the blending amount of fused silica and suppress the increase in the melt viscosity of the curable composition, it is preferable to mainly use spherical ones. 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 rate is preferably blended within the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

In addition, the curable resin composition of the present invention is used for conductive paste, etc. In the case of the route, conductive fillers such as silver powder or copper powder can be used.

As described in detail above, the epoxy resin of the present invention has the characteristics of excellent heat resistance and extremely low dielectric loss tangent. In addition, its solubility in general-purpose organic solvents, or curing properties with various hardeners and other resin materials require high enough general requirements, except for printed wiring boards, semiconductor sealing materials, resist materials, etc. 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 preferable to mix and use an organic solvent for dilution. The above-mentioned organic solvents include: methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellulose, ethyl diethylene glycol ethyl Ester, propylene glycol monomethyl ether acetate, etc. 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 use of printed wiring boards, methyl ethyl ketone, acetone, dimethylformamide, and cyclohexanone are preferred. The polar solvent with an isoboiling point of 160° C. or less is preferably used in a ratio of 25 to 80% by mass of non-volatile components. In the application of build-up adhesive film, it is preferable to use ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, carbitol Acetate solvents such as acetate; carbitol solvents such as celluloid and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide, N- Methylpyrrolidone, etc.; preferably used at a ratio of 25-60% by mass of non-volatile components.

In addition, the method for manufacturing a printed wiring board using the curable resin composition of the present invention may include, for example, the following method: impregnating a reinforcing base material with a curable resin composition and curing it to obtain a prepreg, superimposing it on a copper foil and combining it Perform heating and crimping. The above-mentioned reinforcing substrates can include: Paper, glass cloth, glass non-woven fabric, polyaramide paper, polyaramide cloth, glass mat, glass roving cloth, etc. The amount of the curable resin composition impregnated is not particularly limited, but it is usually preferably prepared so that the resin component in the prepreg becomes 20-60% by mass.

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

[Example]

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

GPC measurement conditions

Measuring device: "HLC-8320GPC" manufactured by Tosoh Co., Ltd., column: protection column "HXL-L" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GE LG2000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

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

Measurement conditions: column temperature 40℃

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

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

(Use polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

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

Example 1: Production of epoxy resin (1) solution

Add 202 parts by mass of m-xylylene chloride and 1,250 parts by mass of toluene to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer, and perform decompression nitrogen replacement in the reaction system to dissolve them . Then, 288 parts by mass of 1-naphthol was added, and the reaction system was replaced with nitrogen under reduced pressure to dissolve it. Next, 0.6 parts by mass of tetrabutylammonium bromide was added, and while nitrogen flushing was performed, the inside of the reaction system was controlled below 60° C., and 400 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After the dropwise addition, the stirring was continued for 1 hour for reaction. After the reaction, the reaction mixture was left to stand for liquid separation, and the water layer was removed. Water was added to the remaining organic layer and stirred for about 15 minutes for mixing. After that, the mixture was allowed to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the water layer became 7, and thereafter, heating and reduced pressure drying was performed to obtain 395 parts by mass of an ester compound (A-1) represented by the following structural formula (a).

Add bisphenol A epoxy resin ("EXA-850CRP" manufactured by DIC Co., Ltd., epoxy equivalent 173g/equivalent) to a flask equipped with a thermometer, dropping funnel, condenser, shunt tube, and 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 the reaction system under reduced pressure nitrogen substitution. Then, 0.15 parts by mass of dimethylaminopyridine was added, while nitrogen flushing was performed, While raising the temperature in the reaction system to 150°C. After making it react at 150 degreeC for 24 hours, 285 mass parts of cyclohexanone and 450 mass parts of methyl ethyl ketones were added and diluted, and 1220 mass parts of epoxy resin (1) solutions were obtained. The epoxy equivalent of the epoxy resin (1) is 19,450 g/equivalent, the weight average molecular weight (Mw) is 37,180, and the molecular weight distribution (Mw/Mn) is 9.3. The GPC line diagram of the obtained epoxy resin (1) is shown in FIG. 1.

Example 2: Production of epoxy resin (2) solution

Add dihydroxy naphthalene type epoxy resin ("HP-4032D" manufactured by DIC Co., Ltd., epoxy equivalent 141g/equivalent) to a flask equipped with a thermometer, dropping funnel, condenser, shunt tube, and 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 the reaction system by purging with nitrogen under reduced pressure. Then, 0.07 parts by mass of dimethylaminopyridine was added, and while nitrogen flushing was performed, the inside of the reaction system was heated to 150°C. 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 equivalent of the epoxy resin (2) is 34,860 g/equivalent, the weight average molecular weight (Mw) is 23,940, and the molecular weight distribution (Mw/Mn) is 6.8. The GPC line diagram of the obtained epoxy resin (2) is shown in FIG. 2.

Example 3: Production of epoxy resin (3) solution

Add 66 parts by mass of alicyclic epoxy resin ("CEL2021P" manufactured by Daicel Co., Ltd., epoxy equivalent 130g/equivalent) to a flask equipped with a thermometer, dropping funnel, condenser, shunt tube, and stirrer , 105 parts by mass of the ester (A-1) obtained previously, and 73 parts by mass of cyclohexanone were dissolved in the reaction system by nitrogen substitution under reduced pressure. Then, 0.07 parts by mass of dimethylaminopyridine was added, and while nitrogen flushing was performed, the inside of the reaction system was elevated. Warm to 150°C. 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 equivalent of the epoxy resin (3) is 8,210 g/equivalent, the weight average molecular weight (Mw) is 10,000, and the molecular weight distribution (Mw/Mn) is 5.7. The GPC line diagram of the obtained epoxy resin (3) is shown in FIG. 3.

Example 4: Production of epoxy resin (4) solution

型環氧化合物為主成分之環氧樹脂(環氧基當量265g/當量)136質量份、先前所得之酯化物(A-1)105質量份、環己酮103質量份，於反應系統內進行減壓氮氣置換而使之溶解。繼而，加入二甲基胺基吡啶0.10質量份，一面實施氮氣沖洗，一面將反應系統內升溫至150℃。於150℃使之反應12小時後，加入環己酮178質量份與甲基乙基酮281質量份而進行稀釋，從而獲得環氧樹脂(4)溶液750質量份。環氧樹脂(4)之環氧基當量為8,520g/當量，重量平均分子量(Mw)為23,530，分子量分布(Mw/Mn)為8.3。將所得到之環氧樹脂(4)之GPC線圖示於圖4。 Add the following structural formula (b) to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a shunt tube, and a stirrer

136 parts by mass of epoxy resin (epoxy equivalent of 265g/equivalent) with epoxy compound as the main component, 105 parts by mass of the previously obtained ester compound (A-1), and 103 parts by mass of cyclohexanone are carried out in the reaction system Dissolve by replacing with nitrogen under reduced pressure. Then, 0.10 parts by mass of dimethylaminopyridine was added, and while nitrogen flushing was performed, the temperature in the reaction system was increased to 150°C. After making it react at 150 degreeC for 12 hours, 178 mass parts of cyclohexanone and 281 mass parts of methyl ethyl ketones were added and diluted, and 750 mass parts of epoxy resin (4) solutions were obtained. The epoxy equivalent of the epoxy resin (4) is 8,520 g/equivalent, the weight average molecular weight (Mw) is 23,530, and the molecular weight distribution (Mw/Mn) is 8.3. The GPC line diagram of the obtained epoxy resin (4) is shown in FIG. 4.

Example 5: Production of epoxy resin (5) solution

Add an epoxy resin (epoxy equivalent of 246g) mainly composed of the epoxy resin represented by the following structural formula (c) to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer /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 replaced with nitrogen under reduced pressure in the reaction system to dissolve them. Then, 0.09 parts by mass of dimethylaminopyridine was added, and while nitrogen flushing was performed, the inside of the reaction system was heated to 150°C. 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 equivalent of the epoxy resin (5) is 13,270 g/equivalent, the weight average molecular weight (Mw) is 21,000, and the molecular weight distribution (Mw/Mn) is 5.8. The GPC line diagram of the obtained epoxy resin (5) is shown in FIG. 5.

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

Add bisphenol A epoxy resin ("EPICLON 850-S" made by DIC Co., Ltd., epoxy equivalent 188g/equivalent to a flask equipped with thermometer, dropping funnel, condenser, shunt tube, and stirrer ) 97 parts by mass, 109 parts by mass of bisphenol A dibenzoate, and 88 parts by mass of cyclohexanone were dissolved in the reaction system by nitrogen substitution under reduced pressure. Then, 0.08 parts by mass of dimethylaminopyridine was added, and while nitrogen flushing was performed, the inside of the reaction system was heated to 150°C. 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 equivalent of the epoxy resin (1') is 6,650 g/equivalent, the weight average molecular weight (Mw) is 7,380, and the molecular weight distribution (Mw/Mn) is 2.3.

Examples 6-10 and Comparative Example 1

Film production and evaluation

The epoxy resin solutions obtained in Examples 1 to 5 and Comparative Manufacturing Example 1 were coated on the separator (polysiloxane-treated polyethylene terephthalate film) using a tool, and dried at 80°C for 10 minutes, It was further dried at 150°C for 1 hour to form an epoxy resin film with a thickness of 70 μm. 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.

Heat resistance measurement (DSC-Tg)

For the epoxy resin film made by the above method, the DSC822e manufactured by METTLER TOLEDO is used to measure the DSC-Tg under the condition of 10°C/min.

Measurement of dielectric loss tangent

After heating and vacuum drying the obtained epoxy resin film, it is stored in a room at 23°C and a humidity of 50% for 24 hours. After that, according to JIS-C-6481, use Agilent Technology stock Impedance Material Analyzers "HP4291B" manufactured by Co., Ltd. measure the dielectric loss tangent of epoxy resin film at 1GHz.

Claims (11)

An epoxy resin solution comprising: epoxy resin, and organic solvent, and the epoxy resin is a compound (a1) containing a phenolic hydroxyl group and an aromatic dicarboxylic acid or its acid halide (a2) The ester compound (A) and the bifunctional epoxy compound (B) are necessary raw materials. The average number of functional groups of the epoxy compound in the raw materials is 2.5 or less, and the epoxy equivalent of the epoxy resin is 5,000~100,000g /Equivalent, and the weight average molecular weight (Mw) is 5,000 to 100,000. Such as the epoxy resin solution of item 1 in the scope of patent application, wherein the above-mentioned epoxy resin has a molecular structure represented by the following structural formula,

[In the formula, X is a structural part derived from the phenolic hydroxyl-containing compound (a1), Y is a structural part derived from an aromatic dicarboxylic acid or its acid halide (a2), and Z is a structural part derived from a bifunctional epoxy For the structural part of compound (B), n is an integer representing the number of repeating units]. For example, the epoxy resin solution of item 1 in the scope of the patent application, wherein the reaction ratio of the above-mentioned phenolic hydroxyl-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) is: relative to the above-mentioned aromatic The carboxylic acid or its acid halide (a2) has a total of 1 mol of carboxyl groups or halogenated acyl groups, and the above-mentioned phenolic hydroxyl group-containing compound (a1) is 0.95 to 1.05 mol The ratio. For example, the epoxy resin solution of item 1 in the scope of patent application, wherein the above-mentioned phenolic hydroxyl-containing compound (a1) is 1-naphthol or 2-naphthol. For example, the epoxy resin solution of item 1 in the scope of patent application, wherein the above-mentioned organic solvent is an organic solvent with a boiling point below 160°C. For example, the epoxy resin solution of any one of items 1 to 5 in the scope of patent application has a non-volatile content of 25 to 80% by mass. For example, the epoxy resin solution of item 6 in the scope of patent application, wherein the above-mentioned organic solvent is methyl ethyl ketone, acetone, dimethylformamide or cyclohexanone. A method for producing an epoxy resin solution, in which the phenolic hydroxyl-containing compound (a1) is esterified with an aromatic dicarboxylic acid or its acid halide (a2) (A) at a temperature of 100 to 180°C After reacting with an epoxy compound, an organic solvent is added for dilution, and the above-mentioned epoxy compound requires a bifunctional epoxy compound (B), and the average number of functional groups of the epoxy compound in the raw material is 2.5 or less. For example, the manufacturing method of epoxy resin solution in the scope of the patent application, wherein the use ratio of the above-mentioned phenolic hydroxyl-containing compound (a1) and the aromatic dicarboxylic acid or its acid halide (a2) is: relative to the above The aromatic polycarboxylic acid or its acid halide (a2) has a total of 1 mol of carboxyl groups or halogenated acyl groups, and the above-mentioned phenolic hydroxyl group-containing compound (a1) has a ratio of 0.95 to 1.05 mol. For example, the manufacturing method of epoxy resin solution in item 8 of the scope of patent application, wherein the epoxy equivalent of the epoxy resin in the epoxy resin solution is 5,000~100,000g/equivalent, and the weight The weight average molecular weight (Mw) is 5,000 to 100,000. A method for producing an epoxy resin film, which has the following steps: an epoxy compound containing a bifunctional epoxy compound (B) and a phenolic hydroxyl-containing compound (a1) and an aromatic dicarboxylic acid having an average number of functional groups of 2.5 or less The esterification (A) of acid or its acid halide (a2) is reacted to obtain epoxy resin with epoxy equivalent of 5,000~100,000g/equivalent and weight average molecular weight (Mw) of 5,000~100,000 dissolved in organic The epoxy resin solution obtained from the solvent; and the epoxy resin solution obtained above is coated on the separator and heated and dried.

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