TW201815876A - Active ester resin and cured product thereof - Google Patents

Abstract

Provided are: an active ester resin having high heat resistance and moisture-absorption resistance and having excellent dielectric properties, etc., in a cured product; a curable resin composition containing same; a cured product thereof; a printed wiring board; and a semiconductor sealing material. An active ester resin, a curable resin composition containing same, a cured product thereof, a printed wiring board, and a semiconductor sealing material, said active ester resin being characterized by having, as essential reactive raw materials thereof: (A) a phenolic hydroxyl group-containing compound; (B) a phenol resin having a molecular structure whereby a phenol compound (b) having at least one hydrocarbon group on an aromatic ring is nodular at a methylene group; and (C) an aromatic polycarboxylic acid or an acid halide thereof.

Description

   Active ester resin and its hardened product   

The present invention relates to an active ester resin having high heat resistance or moisture absorption resistance and excellent dielectric properties, a curable resin composition containing the same, 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., with the reduction in thickness of various electronic components or the increase in speed and frequency of signals, development of new resin materials in line with these market trends is being sought. As the properties required for resin materials, of course, there are basic properties such as heat resistance and moisture absorption resistance. During the continuous development of high-speed or high-frequency signals, in order to reduce energy loss caused by heat generation, the dielectric constant of the hardened material Both the dielectric loss tangent and the value of the dielectric loss tangent are also low.

As a resin material having a relatively low dielectric constant and dielectric loss tangent of a hardened material, a technique is known in which an esterification of dicyclopentadiene phenol resin and α-naphthol with phthalyl chloride is used. The obtained active ester resin is used as a hardener for the epoxy resin (see Patent Document 1 below). The active ester resin described in Patent Document 1 has a characteristic that the dielectric constant or the dielectric loss tangent of the hardened material is lower when compared with the case where a conventional type hardener such as a phenol novolac resin is used, but It has not met recent market requirements. In addition, the heat resistance evaluated by the glass transition temperature of the cured product is also required to be further improved.

[Patent Document 1] Japanese Patent Laid-Open No. 2004-169021

Therefore, the problem to be solved by the present invention is to provide an active ester resin having high heat resistance or moisture absorption resistance and excellent dielectric properties, a curable resin composition containing the same, a cured product thereof, and a printed wiring board. And semiconductor sealing materials.

The present inventors conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that an active ester resin using a phenol resin having the following structure as an essential reaction raw material has high heat resistance or moisture absorption resistance and a dielectric property It is also excellent, thus completing the present invention. The phenol resin has a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is connected by a methylene group.

That is, the present invention relates to an active ester resin, which is characterized in that a phenolic hydroxyl group-containing compound (A), a phenol resin (B), and an aromatic polycarboxylic acid or an acid halide (C) thereof are required. As a reaction raw material, the phenol resin (B) has a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is connected by a methylene group.

The present invention further relates to a curable resin composition containing the above active ester 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 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 active ester resin having high heat resistance or moisture absorption resistance and excellent dielectric properties, a hardening resin composition containing the hardened material, a hardened material, a printed wiring board, and a semiconductor sealing material. .

FIG. 1 is a GPC line chart of the active ester resin (1) obtained in Example 1. FIG.

FIG. 2 is a GPC line chart of the active ester resin (2) obtained in Example 2. FIG.

Hereinafter, the present invention will be described in detail.

The active ester resin of the present invention is characterized by comprising a phenolic hydroxyl-containing compound (A), a phenol resin (B) having the following molecular structure, and an aromatic polycarboxylic acid or its acid halide (C As an essential reaction raw material, the phenol resin (B) has a molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is connected by a methylene group.

The compound (A) 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 (A) may be used singly or in combination of two or more kinds. Specific examples of the phenolic hydroxyl-containing compound (A) include phenol, naphthol, anthracenol, and compounds having one or more substituents on their aromatic cores. Examples of the substituent on the aromatic core include methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, Aliphatic hydrocarbon groups such as dodecyl; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy; halogen atoms such as fluorine, chlorine, and bromine; phenyl, naphthyl, and anthracenyl Aryl; aralkyl such as phenylmethyl, phenylethyl, naphthylmethyl, naphthylethyl, and the like.

Among these, from the viewpoint of being an active ester resin having high heat resistance or hygroscopicity and excellent dielectric properties, the phenol compound having one or more hydrocarbon groups on the aromatic ring (a ). The number of hydrocarbon groups on the aromatic ring is preferably 1 or 2. Examples of the hydrocarbon group of the phenol compound (a) on the aromatic ring include the aliphatic hydrocarbon group, the aryl group, and the aralkyl group. Among them, the hardened material has high heat resistance or hygroscopicity, and has a dielectric property. In terms of an active ester resin that is also excellent in characteristics, an aliphatic hydrocarbon group or an aryl group is preferable, and its carbon number is preferably in a range of 1 to 12. Furthermore, it is more preferable that the aliphatic hydrocarbon group has a branched structure. In this case, the number of carbon atoms is preferably in a range of 3 to 12. Specific examples of the aliphatic hydrocarbon group having a branched structure include isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, third pentyl, and third octyl Wait.

Regarding the phenol resin (B), examples of the hydrocarbon group of the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring include methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, Aliphatic hydrocarbon groups such as cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl; aryl groups such as phenyl, naphthyl, and anthryl; phenylmethyl, phenylethyl , Aralkyl groups such as naphthylmethyl, naphthylethyl, and the like. Among them, in terms of being an active ester resin having high heat resistance or moisture absorption resistance and excellent dielectric properties, the above-mentioned hydrocarbon group is preferably an aliphatic hydrocarbon group or an aryl group, and the number of carbon atoms thereof is preferably 1 Range of ~ 12. The number of hydrocarbon groups on the aromatic ring is preferably 1 or 2. Furthermore, it is more preferable that the aliphatic hydrocarbon group has a branched structure. In this case, the number of carbon atoms is preferably in a range of 3 to 12. Specific examples of the aliphatic hydrocarbon group having a branched structure include isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, third pentyl, and third octyl Wait.

As a specific example of the phenol resin (B) having a molecular structure of "the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring is connected by a methylene group", for example, one or more of the above-mentioned aromatic rings have one Polycondensate of a hydrocarbon-based phenol compound (b) and formaldehyde.

The polycondensate of the phenol compound (b) and formaldehyde can be produced, for example, by the same method as in the production of a normal phenol novolac resin. Specifically, a method may be mentioned in which the phenol compound (b) and formaldehyde are reacted in the presence of an acid catalyst at a temperature of 100 to 200 ° C. After the reaction, if necessary, the above-mentioned phenol compound (b) may be removed by distillation. The unreacted phenol compound in the reaction mixture can also be used as the phenolic hydroxyl-containing compound (A) as it is.

The formaldehyde used in the above method can be used as a formalin solution or as paraformaldehyde. The reaction ratio of the phenol compound (b) to the aldehyde is preferably a ratio of formaldehyde in the range of 0.01 to 0.9 mol, relative to 1 mol of the phenol compound (b), in terms of easy control of the reaction.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. These can be used individually or in combination of 2 or more types. The use amount of these acid catalysts is preferably in the range of 0.1 to 5% by mass based on the total mass of the reaction raw materials.

The reaction between the phenol compound (b) and formaldehyde may be performed in an organic solvent, if necessary. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above-mentioned temperature conditions. Specific examples include methylcellulose, ethylcellulose, toluene, xylene, and formazan. Isobutyl ketone and the like. When using these organic solvents, it is preferable to use it in the range of 10-500 mass% with respect to the total mass of a reaction raw material.

In the reaction between the phenol compound (b) and formaldehyde, various antioxidants or reducing agents may be used in order to suppress the coloring of the novolac resin obtained. Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and trivalent phosphorus atom-containing phosphite compounds. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrogen sulfite, salts thereof, and zinc.

After completion of the reaction, the reaction mixture may be subjected to neutralization treatment or water washing, and thereafter, unreacted reaction raw materials or by-products may be distilled off to obtain the target phenol resin (B).

The hydroxyl equivalent of the phenol resin (B) is preferably in the range of 110 to 250 g / equivalent in terms of being an active ester resin having high solvent solubility and being easily used in various applications. The softening point of the phenol resin (B) is preferably in the range of 40 to 130 ° C.

The aromatic polycarboxylic acid or its acid halide (C) is an aromatic compound capable of forming an ester bond by reacting with the phenolic hydroxyl group-containing compound (A) and the phenolic hydroxyl group of the phenol resin (B). , The specific structure is not particularly limited, and may be any compound. Specific examples include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid; benzenetricarboxylic acids such as 1,2,4-benzenetricarboxylic acid; naphthalene-1,4-dicarboxylic acid and naphthalene- Naphthalene dicarboxylic acids such as 2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid; the acidic halides of these, and the aromatic cores of these are subjected to the above fats Substituted compounds such as a hydrocarbon group, an alkoxy group, and a halogen atom. Examples of the acid halide include osmium chloride, osmium bromide, osmium fluoride, and osmium iodide. These can be used individually or in combination of 2 or more types. Among them, a phthalic acid such as isophthalic acid or terephthalic acid or an acidic halide thereof is preferred in terms of being an active ester resin having high reactivity and excellent curability.

The reaction of the phenolic hydroxyl-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or its acid halide (C) can be performed, for example, by the following method: in the presence of an alkali 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.

The reaction ratio of the phenolic hydroxyl-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or its acid halide (C) can be appropriately changed according to the required molecular design. Among them, in terms of being an active ester resin having high solvent solubility and being easily used in various applications, the molar number (A _OH ) of the hydroxyl group of the phenolic hydroxyl group-containing compound (A) is preferred. The ratio of the number of moles (B _OH ) of hydroxyl groups in the above phenol resin (B) [(A _OH ) / (B _OH )] is a ratio of 10/90 to 75/25, more preferably 20/80 to 50/50 ratio. In addition, it is preferable that the amount of hydroxyl groups contained in the phenolic hydroxyl-containing compound (A) is 1 mole relative to the total of the carboxyl group or the sulfonyl halide group contained in the aromatic polycarboxylic acid or its acid halide (C). The sum of the number of ears and the number of moles of the hydroxyl groups in the phenol resin (B) is 0.9 to 1.1 moles.

The active ester resin of the present invention may contain an ester compound (AC) of the above-mentioned phenolic hydroxyl group-containing compound (A) and the above-mentioned aromatic polycarboxylic acid or its acid halide (C). The ester compound (AC) can be adjusted, for example, by adjusting the reaction ratio of the phenolic hydroxyl-containing compound (A), the phenol resin (B), and the aromatic polycarboxylic acid or its acid halide (C). Manufactured as a component of an active ester resin.

As an example of the specific structure of the above-mentioned ester compound (AC), for example, the following structure is exemplified in the following structural formula (1), that is, a phenol compound (a) having one or more hydrocarbon groups on an aromatic ring is used as the above When the phenolic hydroxyl-containing compound (A) is used, and a benzene dicarboxylic acid or its acid halide is used as the aromatic polycarboxylic acid or its acid halide (C). In addition, the following structural formula (1) is merely an example of a specific structure of the above-mentioned ester compound (AC), and does not exclude diester compounds having other molecular structures.

(In the formula, R ¹ each independently represents a hydrocarbon group, and may be bonded to any carbon atom on a benzene ring, and n is an integer of 0 or 1 to 5)

When the active ester resin contains the above-mentioned ester compound (AC), its content is preferably less than 40% of the active ester resin, and more preferably 0.5 to 30%.

The content of the ester compound (AC) in the active ester resin is a value calculated based on the area ratio of the GPC line graph measured under the following conditions.

Measuring device: "HLC-8220GPC" manufactured by Tosoh Co., Ltd., and column: Protective column "HXL-L" manufactured by Tosoh Co., Ltd.

+ TSK-GEL G2000HXL manufactured by Tosoh Corporation

+ TSK-GEL G2000HXL manufactured by Tosoh Corporation

+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ℃

Tetrahydrofuran

Flow rate 1.0ml / min

Standard: According to the above-mentioned "GPC-8020 Model II Version 4.10" 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 tetrahydrofuran solution of 1.0% by mass in terms of the solid content of the resin was filtered through a microfilter to obtain (50 μl)

The functional group equivalent of the active ester resin of the present invention is preferably in the range of 150 to 350 g / equivalent in terms of being an active ester resin with low curing shrinkage and excellent curability. In the present invention, the functional group in the active ester resin refers to an ester bond site and a phenolic hydroxyl group in the active ester resin. The functional group equivalent of the active ester resin is a value calculated based on the amount of the reaction raw material added.

The softening point of the active ester resin of the present invention is a value measured based on JIS K7234 and is preferably in the range of 85 to 160 ° C, and more preferably in the range of 100 to 150 ° C.

The curable resin composition of the present invention contains the above-mentioned active ester resin and a curing agent. The hardening agent may be any compound that can react with the active ester resin of the present invention, and various compounds can be used without particular limitation. An example of the curing agent is epoxy resin.

Examples of the epoxy resin include a phenol novolac epoxy resin, a cresol novolac epoxy resin, a naphthol novolac epoxy resin, a bisphenol novolac epoxy resin, and a biphenol novolac epoxy resin. Resin, bisphenol epoxy resin, biphenyl epoxy resin, triphenol methane epoxy resin, tetraphenol ethane epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, phenol aromatic Alkyl epoxy resin, naphthol aralkyl epoxy resin and the like.

When an epoxy resin is used as the hardener, other hardeners for epoxy resins may be used in addition to the active ester resin of the present invention. Examples of other hardeners for epoxy resins used herein include diaminodiphenylmethane, diethylenetriamine, triethylenetriamine, diaminodiphenylphosphonium, isophoronedi Amine compounds such as amines, imidazoles, BF ₃ -amine complexes, guanidine derivatives; dicyandiamines, polyamine resins such as linolenic acid dimer and ethylenediamine; Phthalic anhydride, 1,2,4-trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl dianhydride ( methyl nadic anhydride), hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and other anhydrides; phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, Biphenol novolak resin, dicyclopentadiene-phenol addition molding resin, phenol aralkyl resin, naphthol aralkyl resin, trisphenol methane type resin, tetraphenol ethane type resin, amine tris Modified phenol resins such as phenol resins.

The blending ratio of the active ester resin, epoxy resin, and other hardener composition for epoxy resin of the present invention is preferably the following ratio: The above active ester resin is relative to the total of 1 mol of epoxy groups in the epoxy resin. The total of functional groups in other hardeners for epoxy resins is 0.7 to 1.5 moles.

In addition, the curable resin composition of the present invention may contain a cyanate resin, a bismaleimide resin, and a 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 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: inorganic phosphorus compounds such as red phosphorus, ammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and ammonium phosphate; phosphoric acid ester compounds, phosphonic acid compounds, and phosphinic acid acid) compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (9,10-dihydro- 9-oxa-10-phospha phenanthrene-10-oxide), 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphophenanthrene-10-oxide, 10- (2,7 -Dihydroxynaphthyl) Organic compounds such as cyclic organic phosphorus compounds such as 10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resin or phenol resin 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 mix | 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 above-mentioned fused silica is preferred. The fused silica may be used in either a crushed or 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 preferred 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 active ester resin of the present invention has the following characteristics: the cured product has high heat resistance or moisture absorption resistance, and has excellent dielectric properties. In addition, it is one that is generally high in required properties such as solubility in commonly used organic solvents, or hardening properties with epoxy resins, 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. Acetate, 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 use of printed wiring boards, the boiling point of methyl ethyl ketone, acetone, and dimethylformamide is preferably 160. It is preferred to use a polar solvent at a temperature of not more than 40 ° C at a ratio of 40 to 80% by mass of nonvolatile matter. 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 are preferably used at a ratio of 30 to 60% by mass of nonvolatile matter.

In addition, the 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 composition and curing it to obtain a prepreg, which is overlapped with a copper foil and heated. Crimp. 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 content 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 containing the active ester resin of the present invention, a hardener, an inorganic filler, and other optional components 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, molding the semiconductor sealing material using a casting or transfer molding machine, an injection molding machine, etc., and further heating at a temperature of 50 to 200 ° C for 2 to 10 hours. With this method, a semiconductor device that is a molded article can be obtained.

[Example]

Next, the present invention will be described more specifically with reference to examples and comparative examples. Unless otherwise specified, the “parts” and “%” in the examples are quality standards. The GPC measurement conditions in this example are as follows.

◆ GPC measurement conditions

Measuring device: "HLC-8220 GPC" manufactured by Tosoh Co., Ltd., and column: Protective column "HXL-L" manufactured by Tosoh Co., Ltd.

+ TSK-GEL G2000HXL manufactured by Tosoh Corporation

+ TSK-GEL G2000HXL manufactured by Tosoh Corporation

+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ℃

Tetrahydrofuran

Flow rate 1.0ml / min

Standard: According to the above-mentioned "GPC-8020 Model II Version 4.10" 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 tetrahydrofuran solution of 1.0% by mass in terms of the solid content of the resin was filtered through a microfilter to obtain (50 μl)

Example 1 Production of activated ester resin (1)

To a flask equipped with a thermometer, a dropping funnel, a condenser tube, a shunt tube, and a stirrer, 234.3 parts by mass of p-tert-butylphenol, 52.8 parts of toluene, 52.8 parts by mass of 37% by mass aqueous formalin solution, and 49% hydroxide were added. 4.8 parts by mass of sodium was heated from room temperature to 75 ° C. while stirring, and the reaction was performed by stirring at the same temperature for 1 hour. After the reaction was completed, 7.1 parts by mass of sodium dihydrogen phosphate was added for neutralization, 363.2 parts by mass of toluene was added, and washing was performed three times with 121.1 parts by mass of water. 234.8 parts by mass of a mixture (1) containing unreacted p-third butylphenol and a phenol resin (B-1) was dried under heating and reduced pressure. The hydroxyl equivalent of the mixture (1) was 155 g / equivalent.

In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a shunt tube, and a stirrer, 141.4 parts by mass of m-xylylenedichloride and 1,000 parts by mass of toluene were added, and depressurized nitrogen was substituted in the system to make them. Dissolve. Then, 217.0 parts by mass of the previously obtained mixture (1) was added, and dissolved under reduced pressure nitrogen substitution in the system. 0.4 part by mass of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while 280 parts by mass of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours while performing nitrogen flushing. 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. 307.3 parts by mass of water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes. Thereafter, the mixture was left 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 then it was dried under the conditions of heating and reduced pressure to obtain 298.1 parts by mass of the active ester resin (1). The functional group equivalent of the active ester resin (1) was 220 g / equivalent, and the softening point measured based on JIS K7234 was 132 ° C. The content of bis (p-tert-butylphenyl) metaphthalate in the active ester resin (1) calculated from the GPC chart was 10.1%.

Example 2 Production of Active Ester Resin (2)

321.9 parts by mass of p-octylphenol, 52.8 parts by mass of toluene, 52.8 parts by mass of 37% by mass aqueous formalin solution, and 49% hydrogen were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer. 6.6 parts by mass of sodium oxide was heated from room temperature to 75 ° C, and the reaction was carried out by stirring at the same temperature for 1 hour. After the reaction was completed, 9.7 parts by mass of sodium dihydrogen phosphate was added for neutralization, 494.6 parts by mass of toluene was added, and washing was performed three times with 164.9 parts by mass of water. It was dried under heating and reduced pressure to obtain 319.8 parts by mass of a mixture (2) containing unreacted p-octylphenol and phenol resin (B-2). The hydroxyl equivalent of the mixture (2) was 211 g / equivalent.

In Example 1, except having changed to 295.4 parts by mass of the mixture (2) instead of 217.0 parts by mass of the mixture (1), 374.8 parts by mass of the active ester resin (2) was obtained in the same manner as in Example 1. The functional group equivalent of the active ester resin (2) was 276 g / equivalent, and the softening point measured based on JIS K7234 was 101 ° C. The content of bis (p-third octylphenyl) metaphthalate in the active ester resin (2) calculated from the GPC chart was 14.8%.

Comparative Production Example 1 Production of Active Ester Resin (1 ')

In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a shunt tube, and a stirrer, add 165 parts by mass of an addition reaction product of dicyclopentadiene and phenol (hydroxyl equivalent 165 g / equivalent, softening point 85 ° C), 72 parts by mass of 1-naphthol and 630 parts by mass of toluene were dissolved under reduced pressure nitrogen substitution in the system. Then, 152 parts by mass of m-xylylenedichloride was added, and the solution was dissolved while being subjected to reduced-pressure nitrogen substitution in the system. While purging with nitrogen, the inside of the system was controlled below 60 ° C, and 210 g 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 then toluene and the like were distilled off under heating and reduced pressure conditions to obtain an active ester resin (1 ′). The functional group equivalent of the active ester resin (1 ') was 223 g / equivalent, and the softening point measured based on JIS K7234 was 150 ° C.

Examples 3, 4 and Comparative Example 1

Active ester resin, epoxy resin (*), and dimethylaminopyridine were blended in the proportion shown in Table 1 below, and nonvolatile matter was adjusted to 58% by mass using methyl ethyl ketone to obtain hardenability. Resin composition. Various evaluation tests were performed on the obtained curable resin composition according to the following points. The results are shown in Table 1.

Epoxy resin (*): Dicyclopentadiene modified phenol type epoxy resin ("EPICLON HP-7200H" manufactured by DIC Corporation, epoxy equivalent 277g / equivalent)

Production of laminated boards

A laminated board was produced under the following conditions.

Base material: Glass cloth "# 2116" (210 × 280mm) made by Nitto Textile Co., Ltd.

Line layers: 6

Pre-soaking condition: 160 ℃

Hardening conditions: 200 ° C, 40kg / cm ² and 1.5 hours

Thickness after forming: 0.8mm

Determination of glass transition temperature

The previously obtained laminated board was cut into a size of 5 mm in width and 54 mm in length. As a test piece, a viscoelasticity measuring device ("Solid Viscoelasticity Measuring Device RSAII" manufactured by Rheometrics) was used. Under the measurement conditions of the temperature increase rate of 3 ° C / min, the temperature at which the change in the elastic modulus reached the maximum (the maximum change rate of tan δ) was evaluated as the glass transition temperature.

Measurement of dielectric constant and dielectric loss tangent

For laminated boards stored in a room at 23 ° C and 50% humidity for 24 hours after heating and vacuum drying, according to JIS-C-6481, the Impedance Material Analyzers "HP4291B" manufactured by Agilent Technology Co., Ltd. are used to measure the dielectric constant at 1 GHz And dielectric loss tangent.

Evaluation of moisture absorption

The previously obtained laminated board was cut into a width of 25 mm and a length of 75 mm, and this was used as a test piece, and it was left to stand in an environment of 85 ° C./85% RH for 168 hours to perform a moisture absorption test. The mass of the test piece before and after the test was measured, and the weight change rate was evaluated as the moisture absorption rate.

Claims (9)

    An active ester resin comprising a phenolic hydroxyl-containing compound (A), a phenol resin (B), and an aromatic polycarboxylic acid or its acid halide (C) as essential reaction raw materials. The phenol resin (B) has : A molecular structure in which a phenol compound (b) having one or more hydrocarbon groups on an aromatic ring is connected by a methylene group.         For example, the active ester resin according to item 1 of the application, wherein the phenol resin (B) is a polycondensate of a phenol compound (b) having one or more hydrocarbon groups on the aromatic ring and formaldehyde.         For example, the active ester resin according to item 1 of the application, wherein the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring has a hydrocarbon group of 1 to 12 carbon atoms or an aliphatic hydrocarbon group.         For example, the active ester resin according to item 1 of the patent application range, wherein the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring is a hydrocarbon group having a para position to the phenolic hydroxyl group.         For example, the active ester resin according to item 1 of the application, wherein the phenolic hydroxyl-containing compound (A) and the phenol compound (b) having one or more hydrocarbon groups on the aromatic ring are the same compound.         A curable resin composition containing the active ester resin according to any one of claims 1 to 5 and a curing agent.         A cured product is a cured product of a curable resin composition according to item 6 of the patent application.         A printed wiring board is made by using a curable resin composition according to claim 6 of the patent application.         A semiconductor sealing material is made by using a hardening resin composition in the scope of patent application No. 6.