TW201904930A - Active ester compound and hardenable composition - Google Patents

Abstract

The purpose of the present invention is to provide an active ester compound having a low elastic modulus under high-temperature conditions in a cured product, a curable composition containing the active ester compound, a cured product thereof, a semiconductor sealing material, and a printed wiring board. Provided are an active ester compound that is a diesterified product of a dihydroxynaphthalene compound (a1) and an aromatic monocarboxylic acid or an acid halide thereof (a2), a curable composition containing the active ester compound, a cured product thereof, a semiconductor sealing material, and a printed wiring board. The active ester compound is characterized by having a low elastic modulus under high-temperature conditions in the cured product.

Description

   Active ester compound and hardening composition   

The present invention relates to an active ester compound having a low elastic modulus under high temperature conditions, a curable composition containing the active ester compound, a cured product thereof, a semiconductor sealing material, and a printed wiring board.

In the technical field of insulating materials used in semiconductors, multilayer printed boards, etc., along with the thinning or miniaturization of various electronic components, it is required to develop novel resin materials that match these market trends. As a performance required for a semiconductor sealing material, a low elastic modulus under high temperature conditions is required to improve reflow solderability. In addition, the heat resistance or moisture absorption resistance of the hardened material is of course important. As a countermeasure against high-speed and high-frequency signals, it is important that the dielectric constant and dielectric loss tangent of the hardened material are low. In other words, it is important that physical properties such as glass transition temperature (Tg) do not change, and as a countermeasure against warpage or deformation accompanying thinning, it is also important to have a low curing shrinkage rate or a linear expansion coefficient.

As a resin material excellent in heat resistance and dielectric properties of a cured product, a technique using isophthalic acid bis (1-naphthyl ester) as a curing agent for an epoxy resin is known (see Patent Document 1 below). The epoxy resin composition described in Patent Document 1 uses isophthalic acid bis (α-naphthyl ester) as an epoxy resin hardener, and uses a conventional epoxy resin hardener such as a phenol novolac resin. Compared with the situation, the value of the dielectric constant or dielectric loss tangent of the hardened material is indeed lower, but the elastic modulus of the hardened material under high temperature conditions does not meet the level required in recent years. In addition, since the melt viscosity is high, there is a limit to use in applications requiring low melt viscosity such as a semiconductor sealing material.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-82063

Therefore, an object of the present invention is to provide an active ester compound having a low elastic modulus under high temperature conditions, a curable composition containing the active ester compound, a cured product thereof, a semiconductor sealing material, and a printed wiring board.

The present inventors made intensive studies in order to solve the above-mentioned problems, and as a result, they found that the active ester compound, which is a diester of a dihydroxynaphthalene compound and an aromatic monocarboxylic acid or an acid halide thereof, is not only hardened under high temperature conditions The elastic modulus is low and the melt viscosity is also low, thereby completing the present invention.

That is, this invention relates to an active ester compound which is a diester of a dihydroxy naphthalene compound (a1) and an aromatic monocarboxylic acid or its acid halide (a2).

The present invention further relates to a curable composition containing the above active ester compound and a curing agent.

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

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

The present invention further relates to a printed wiring board using the above-mentioned curable composition.

According to the present invention, it is possible to provide an active ester compound having a low elastic modulus of a cured product under high temperature conditions, a curable composition containing the cured ester compound, a cured product thereof, a semiconductor sealing material, and a printed wiring board.

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

Hereinafter, the present invention will be described in detail.

The active ester compound of the present invention is a diester of a dihydroxynaphthalene compound (a1) and an aromatic monocarboxylic acid or an acid halide (a2) thereof.

Examples of the dihydroxynaphthalene compound (a1) include a dihydroxynaphthalene compound and a dihydroxynaphthalene compound having one or more substituents on the aromatic ring of the dihydroxynaphthalene. Examples of the substituent include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. The aliphatic hydrocarbon group may be any of a linear type and a branched type, and may have an unsaturated bond in the structure. Specific examples include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; cycloalkyl groups such as cyclohexyl; and unsaturated bonds such as vinyl, allyl, and propargyl Base etc. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a structural site in which an aromatic nucleus is substituted with an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, or the like. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and a structural site in which an aromatic nucleus is substituted with the alkyl group, alkoxy group, or halogen atom. . The substitution positions of two hydroxyl groups in the dihydroxynaphthalene compound (a1) are not particularly limited. Examples include 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,8- Dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4-dihydroxynaphthalene, and the like. The said dihydroxynaphthalene compound (a1) may be used individually by 1 type, and may use 2 or more types together.

Among the dihydroxynaphthalene compounds (a1), 1,6-dihydroxynaphthalene is preferred in terms of being an active ester compound having a low modulus of elasticity of the cured product under high temperature conditions and excellent curing properties. Compound or 2,7-dihydroxynaphthalene compound.

Examples of the aromatic monocarboxylic acid or its acid halide (a2) include benzenecarboxylic acid, naphthalenecarboxylic acid, and one or more aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, Compounds such as substituents such as alkyl, aralkyl, and the like, such as acid halides. These may be used individually by 1 type, and may use 2 or more types together. Among them, benzenecarboxylic acid or a halide thereof is preferred in terms of being an active ester compound having a low modulus of elasticity under high temperature conditions and excellent curing properties. Therefore, as a more preferable structure of the active ester compound of this invention, the thing represented by the following structural formula (1) is mentioned.

(In the formula, R ^{1 is} each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and may be bonded to any carbon atom forming a naphthalene ring; R ^{2 is} each independently Is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group, and may be bonded to any carbon atom forming a benzene ring; m is an integer of 0 or 1 to 6, and n is 0 or (Integer from 1 to 5)

The reaction of the dihydroxynaphthalene compound (a1) with the aromatic monocarboxylic acid or its acid halide (a2) can be performed by heating and stirring at a temperature of about 40 to 65 ° C in the presence of an alkali catalyst. Method. The reaction can also be carried out in an organic solvent as necessary. In addition, 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 in the form of an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide having a high catalytic ability is preferable.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether Acetate solvents such as acetate and carbitol acetate; carbitol solvents such as cellulose and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide and dimethyl Ethylacetamide, N-methylpyrrolidone and the like. These can be used individually or in the form of a mixture of two or more solvents.

Regarding the reaction ratio of the above-mentioned dihydroxynaphthalene compound (a1) to the aromatic monocarboxylic acid or its acid halide (a2), in terms of obtaining a target active ester compound in a high yield, it is preferably relative to the above-mentioned dihydroxy group. The naphthalene compound (a1) has a total of 1 mol of hydroxyl groups, and the aromatic monocarboxylic acid or its acid halide (a2) has a ratio of 0.95 to 1.05 mol.

The melt viscosity of the above active ester compound is preferably in the range of 0.01 to 50 dPa · s, and more preferably in the range of 0.01 to 5 dPa · s, according to ASTM D4287 and measured at 150 ° C by an ICI viscometer.

The curable composition of the present invention may contain the above-mentioned active ester compound of the present invention together with other active ester compounds. Examples of the other active ester compounds include ester compounds of a compound having one phenolic hydroxyl group and an aromatic polycarboxylic acid or an acid halide thereof in a molecular structure; polyhydroxybenzene and an aromatic monocarboxylic acid or an acid halide thereof. Esters of compounds; compounds with one phenolic hydroxyl group in the molecular structure, aromatic polycarboxylic acids or their acid halides, and esters of compounds with two or more phenolic hydroxyl groups in the molecular structure; A carboxylic acid or an acid halide thereof, a compound having two or more phenolic hydroxyl groups in a molecular structure, an ester of an aromatic monocarboxylic acid or an acid halide thereof, and the like.

In the case of using the other active ester compounds described above, in terms of fully exerting the effects of the present invention, the ratio of the active ester compound of the present invention to the total of the active ester compound of the present invention and other active ester compounds, It is preferably 80% by mass or more, and more preferably 90% by mass or more. In addition, the melt viscosity of the formulation of the active ester compound of the present invention and other active ester compounds is preferably in the range of 0.01 to 50 dPa · s, and particularly preferably in the range of 0.01 to 5 dPa · s. The melt viscosity of the formulation is a value at 150 ° C as measured by an ICI viscometer in accordance with ASTM D4287.

The curable composition of the present invention contains the above-mentioned active ester compound and a curing agent. The hardener is not particularly limited as long as it is a compound capable of reacting with the active ester compound, and various compounds can be applied. 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.

In the curable composition of the present invention, the blending ratio of the active ester compound and the curing agent is not particularly limited, and it may be appropriately adjusted depending on the required properties of the cured product and the like. As an example of the case where an epoxy resin is used as a curing agent, it is preferable that the total of the functional groups in the active ester compound is 0.7 to 1.5 with respect to the total of 1 mol of epoxy groups in the curable composition. Mohr's ratio.

The curable composition of the present invention may further contain other resin components. Examples of other resin components include diaminodiphenylmethane, diethylene triamine, triethylene tetramine, diamino diphenylsulfonium, isophorone diamine, imidazole, and BF ₃ -amine. Amines such as complexes and guanidine derivatives; diamine compounds such as dicyandiamide, polyamine resins synthesized from the dimer of linolenic acid and ethylenediamine; phthalic anhydride, Trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, methylnadic acid anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and other anhydrides; cyanate resins; bismaleimide resins; benzo Resin; styrene-maleic anhydride resin; allyl-containing resin typified by diallyl bisphenol or triallyl isocyanurate; polyphosphate or phosphate- Carbonate copolymers, etc. These can be used individually or in combination of 2 or more types. The blending ratio of these other resin components is not particularly limited, and may be adjusted as appropriate depending on the required properties of the hardened material.

The hardenable 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 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). Among the imidazole compounds, 2-ethyl-4-methylimidazole is preferred, and among the pyridine compounds, 4-dimethylaminopyridine is preferred.

Examples of the flame retardant include: inorganic phosphorus compounds such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphatidamine; phosphoric acid ester 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, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydroxynaphthyl) -10H-9-oxa Cyclic organic phosphorus compounds such as -10-phosphaphenanthrene-10-oxide, and organic phosphorus compounds such as derivatives obtained by reacting them with compounds such as epoxy resin or phenol resin; 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 these flame retardants, the range of 0.1-20 mass% in a curable composition is preferable.

The said inorganic filler is prepared, for example, when the curable composition of this invention is used for a semiconductor sealing material use. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, in terms of being able to prepare more inorganic fillers, the above-mentioned fused silica is preferred. The fused silica may be either crushed or spherical. In order to increase the blending 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 one. In order to further increase the amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably formulated in a range of 0.5 to 95 parts by mass out of 100 parts by mass of the curable composition.

When the curable 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 compound and the curable composition containing the active ester compound of the present invention have a feature that the cured product has a low elastic modulus under high temperature conditions. In addition, other general required properties required for resin materials are also sufficiently high, such as solubility in general organic solvents or heat resistance, water absorption resistance, low hardening shrinkage, dielectric properties, etc., and low melt viscosity. Therefore, in addition to electronic materials such as printed wiring boards, semiconductor sealing materials, and resist materials, they can also be widely used in applications such as paints, adhesives, and molded products.

When the curable 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 and dilute it. 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 depending on the use environment of the hardenable composition. For example, in printed wiring board applications, it is preferred that the boiling points such as methyl ethyl ketone, acetone, and dimethylformamide are 160 ° C or lower. The polar solvent is preferably used in such a proportion that the non-volatile content becomes 40 to 80% by mass. In the application of the build-up adhesive film, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone are preferably used; ethyl acetate, butyl acetate, cellulose acetate, propylene glycol monomethyl ether acetate, and carbidine Acetate solvents such as alcohol acetate; carbitol solvents such as cellulose 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 composition of the present invention includes, for example, a method of impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg, which is overlapped with a copper foil. Perform thermal compression bonding. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven cloth, aramid paper, polyaramide cloth, glass felt, glass roving cloth, and the like. The impregnation amount of the curable composition is not particularly limited, and it is usually preferred to prepare the resin composition in the prepreg so that the resin content becomes 20 to 60% by mass.

When the curable composition of the present invention is used for a semiconductor sealing material, it is generally preferred to mix an inorganic filler. The semiconductor sealing material can be prepared by mixing the formulation with an extruder, a kneader, a roll, or the like, for example. The method of forming a semiconductor package using the obtained semiconductor sealing material includes, for example, forming the semiconductor sealing material using a casting or transfer molding machine, an injection molding machine, and the like, and further performing the operation at a temperature of 50 to 200 ° C. 2 A method of heating for ~ 10 hours. By this method, a semiconductor device as 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.

◆ Determination of melt viscosity

In the examples of this case, the melt viscosity of the active ester compound is obtained by measuring the melt viscosity at 150 ° C. using an ICI viscometer in accordance with ASTM D4287.

Example 1 Production of Active Ester Compound (1)

160 g of 1,6-dihydroxynaphthalene and 1100 g of toluene were added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionation tube, and a stirrer, and dissolved while being replaced with nitrogen under reduced pressure in the system. Then, 218 g of benzamidine chloride was added, and the solution was dissolved while being replaced with nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added, and while blowing nitrogen gas, the inside of the system was controlled to 60 ° C. or lower, and 420 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 the completion of the reaction, the reaction mixture was left to stand for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and after stirring and mixing for about 15 minutes, the mixture was left to stand for liquid separation to remove the water layer. This operation was repeated until the pH of the aqueous layer became 7, and then water and toluene were removed by dehydration using a decanter to obtain an active ester compound (1). The melt viscosity of the active ester compound (1) was 0.11 dPa · s.

Example 2 Production of Active Ester Compound (2)

160 g of 2,7-dihydroxynaphthalene and 1100 g of toluene were added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionation tube, and a stirrer, and dissolved while being replaced with nitrogen under reduced pressure in the system. Then, 218 g of benzamidine chloride was added, and the solution was dissolved while being replaced with nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added, and while blowing nitrogen gas, the inside of the system was controlled to 60 ° C. or lower, and 420 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 the completion of the reaction, the reaction mixture was left to stand for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and after stirring and mixing for about 15 minutes, the mixture was left to stand for liquid separation to remove the water layer. This operation was repeated until the pH of the aqueous layer became 7, and then water and toluene were removed by dehydration using a decanter to obtain an active ester compound (2). The melt viscosity of the active ester compound (2) was 0.07 dPa · s.

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

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionation tube, and a stirrer, 202 g of m-xylylenedichloride and 1,250 g of toluene were added, and the solution was dissolved while being replaced with nitrogen under reduced pressure in the system. Then, 288 g of 1-naphthol was added, and it dissolved while carrying out nitrogen substitution under reduced pressure in the system. 0.63 g of tetrabutylammonium bromide was added, and while blowing nitrogen gas, the inside of the system was controlled to 60 ° C or lower, and 420 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 the completion of the reaction, the reaction mixture was left to stand for liquid separation, and the aqueous layer was removed. Water was added to the remaining organic layer, and after stirring and mixing for about 15 minutes, the mixture was left to stand for liquid separation to remove the water layer. This operation was repeated until the pH of the water layer became 7, and then water and toluene were removed by dehydration using a decanter to obtain an active ester compound (1 '). The melt viscosity of the active ester compound (1 ') was 0.65 dPa · s.

Examples 3, 4 and Comparative Example 1

Each component is blended at the ratio shown in Table 1 below to produce a curable composition. The hardenable composition was put into a mold frame, and was molded at a temperature of 175 ° C for 10 minutes using a press. The molded article was taken out of the mold frame, and was cured at a temperature of 175 ° C for 5 hours to obtain a cured article. The hardened | cured material was evaluated by the following procedure. The results are shown in Table 1.

Determination of storage elastic modulus under high temperature conditions

A test piece having a size of 5 mm × 54 mm × 2.4 mm was cut out of the hardened material. For the test piece, a viscoelasticity measuring device ("Solid Viscoelasticity Measuring Device RSAII" manufactured by Rheometric Corporation) was used, and the storage elastic modulus at 260 ° C was measured under conditions of a rectangular tension method, a frequency of 1 Hz, and a temperature rise of 3 ° C / min.

Measurement of flexural modulus and flexural deformation under high temperature conditions

A test piece having a size of 25 mm × 70 mm × 2.4 mm was cut out of the hardened material. For the test piece, a universal material testing machine ("5582" manufactured by Instron) was used, and the bending elastic modulus and bending deformation were measured at a test speed of 1.0 mm / min and a test temperature of 260 ° C.

Epoxy resin (* 1): Cresol novolac epoxy resin ("N-655-EXP-S" manufactured by DIC Corporation, epoxy equivalent 202g / equivalent)

Claims (7)

    An active ester compound, which is a diester of a dihydroxynaphthalene compound (a1) and an aromatic monocarboxylic acid or an acid halide (a2) thereof.     The active ester compound according to claim 1, which has a molecular structure represented by the following structural formula (1), (In the formula, R ^{1 is} each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and may be bonded to any carbon atom forming a naphthalene ring; R ^{2 is} each independently Is any of an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group, and may be bonded to any carbon atom forming a benzene ring; m is an integer of 0 or 1 to 6, and n is 0 or An integer from 1 to 5).     The active ester compound according to claim 1, wherein the dihydroxynaphthalene compound (a1) is a 1,6-dihydroxynaphthalene compound or a 2,7-dihydroxynaphthalene compound.         A hardening composition containing the active ester compound according to any one of claims 1 to 3 and a hardener.         The hardened | cured material is a hardened | cured material of the hardenable composition of Claim 4.         A semiconductor sealing material using the curable composition according to claim 4.         A printed wiring board using the curable composition according to claim 4.