TWI830911B - Multifunctional active ester compounds, resin compositions, cured products and build-up films - Google Patents

Abstract

An object of the present invention is to provide a polyfunctional active ester compound capable of obtaining a resin composition having excellent heat resistance and dielectric properties after curing. Furthermore, an object of the present invention is to provide a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a build-up film using the resin composition. The present invention is a polyfunctional active ester compound represented by the following formula (1). In formula (1), R ¹ and R ² may each be the same or different, and may be an aryl group that may be substituted. X is each independently an oxygen atom or a divalent group, Y is a divalent organic group, n is an integer above 1.

Description

Multifunctional active ester compounds, resin compositions, cured products and build-up films

The present invention relates to a multifunctional active ester compound capable of obtaining a resin composition having excellent heat resistance and dielectric properties after curing. Furthermore, the present invention relates to a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a build-up film using the resin composition.

Curable resins such as epoxy resin that have low shrinkage and excellent adhesion, insulation, and chemical resistance are used in many industrial products. In particular, resin compositions used as interlayer insulating materials for printed wiring boards require dielectric properties such as low dielectric coefficient and low dielectric loss tangent. As a resin composition excellent in such dielectric properties, for example, Patent Documents 1 and 2 disclose a resin composition containing a curable resin and a compound having a specific structure as a curing agent. However, such a resin composition has a problem that it is difficult to achieve both heat resistance and dielectric properties after curing. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-186551 [Patent Document 2] International Publication No. 2016/114286

[Problem to be solved by the invention]

An object of the present invention is to provide a polyfunctional active ester compound capable of obtaining a resin composition having excellent heat resistance and dielectric properties after curing. Furthermore, an object of the present invention is to provide a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a build-up film using the resin composition. [Means used to solve problems]

The present invention is a polyfunctional active ester compound represented by the following formula (1).

In formula (1), R ¹ and R ² may each be the same or different, and may be an aryl group that may be substituted. X is each independently an oxygen atom or a divalent group, Y is a divalent organic group, n is an integer above 1.

The present invention is described in detail below. The present inventors discovered that by using a polyfunctional active ester compound having a specific structure as a curing agent, a resin composition having excellent heat resistance and dielectric properties after curing can be obtained, and completed the present invention.

The polyfunctional active ester compound of the present invention is represented by the above formula (1). In the above formula (1), R ¹ and R ² may each be the same or different, and may be an aryl group that may be substituted. By having an optionally substituted aryl group as the above-mentioned R ¹ and the above-mentioned R ² , the obtained cured product of the resin composition has excellent dielectric properties such as low dielectric loss tangent.

Examples of the aryl group include phenyl, naphthyl, anthracenyl, and the like. Examples of the substituent when the aryl group is substituted include an aliphatic group and the like. Among them, R ¹ and R ² in the above formula (1) are preferably the groups represented by the following formula (2). Since the above R ¹ and the above R ² are groups represented by the following formula (2), when the polyfunctional active ester compound of the present invention is used as a curing agent, the cured product of the resin composition obtained has low dielectric loss. Those with better dielectric properties such as tangent.

In formula (2), R ³ is each independently a hydrogen atom or an aliphatic group, and * is a bonding position.

In the above formula (1), X may be independently different and may be an oxygen atom or a divalent group. Among them, the above-mentioned X is preferably an oxygen atom, a sulfonyl group, a carbonyl group or a group represented by the following formula (3), more preferably an oxygen atom or a group represented by the following formula (3).

In formula (3), * is the bonding position.

In the above formula (1), Y is a divalent organic group. Among them, the above-mentioned Y is preferably an aryl group which may be substituted. Since Y is an aryl group that may be substituted, the resulting cured resin composition has excellent heat resistance.

When Y in the above formula (1) is an aryl group that may be substituted, examples of the aryl group include phenylene group, naphthylene group, anthracenyl group, and the like. Examples of the substituent when the aryl group is substituted include an aliphatic group and the like. Among them, Y in the above formula (1) is preferably 1,3-phenylene group or 1,4-phenylene group.

In the above formula (1), n is an integer of 1 or more. The above-mentioned n is a value such that the number average molecular weight of the polyfunctional active ester compound represented by the above-mentioned formula (1) falls within the range described below, and is preferably 1 or more and 5 or less, and more preferably 1 or 2.

The preferred lower limit of the number average molecular weight of the multifunctional active ester compound of the present invention is 1300, and the preferred upper limit is 5500. By having the above number average molecular weight within this range, the polyfunctional active ester compound of the present invention has better compatibility with the resin component, and the resulting cured resin composition has dielectric properties such as low dielectric loss tangent. More outstanding ones. A more preferred lower limit of the number average molecular weight of the multifunctional active ester compound of the present invention is 1,400, a more preferred upper limit is 2,700, and an even more preferred lower limit is 1,800. In addition, the above-mentioned "number average molecular weight" in this specification is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and calculated in polystyrene conversion. Examples of a column used when measuring the number average molecular weight calculated in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Nippon Analytical Industries, Ltd.).

The polyfunctional active ester compound of the present invention is preferably a compound represented by the following formula (4) since the resulting cured resin composition has particularly excellent heat resistance and dielectric properties.

Examples of a method for producing the polyfunctional active ester compound of the present invention include the following methods. That is, an acid dianhydride represented by the following formula (5), an amine phenol represented by the following formula (6), a dicarboxylic acid represented by the following formula (7), and a dicarboxylic acid represented by the following formula (8-1) can be exemplified. Methods for reacting aromatic monocarboxylic acids and/or aromatic monocarboxylic acids represented by the following formula (8-2), etc. Specifically, the amine phenol represented by the following formula (6) is dissolved in a solvent "which can dissolve the amic acid compound obtained by the reaction" in advance, and the acid dianhydride represented by the following formula (5) is It is added to the obtained solution and allowed to react, thereby obtaining a solution of the amide compound. Examples of the solvent include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and the like. Next, the solvent is removed from the obtained solution of the amide compound by heating or reducing pressure, or the amide oligomer is reprecipitated by adding it to a poor solvent such as water, methanol, or hexane. The mixture is recovered and heated at about 200° C. or higher for 1 hour or more to proceed with the imidization reaction, thereby obtaining an imidization compound having phenolic hydroxyl groups at both ends. Then, the obtained acyl imine compound is subjected to an esterification reaction with a dicarboxylic acid represented by the following formula (7) or a halide thereof. Furthermore, it is esterified with an aromatic monocarboxylic acid represented by the following formula (8-1) or a halide thereof and/or an aromatic monocarboxylic acid represented by the following formula (8-2) or a halide thereof. reaction, the polyfunctional active ester compound of the present invention can be obtained. In addition, the number average molecular weight of the polyfunctional active ester compound of the present invention can be adjusted, for example, by the following method. That is, in the step of reacting the dicarboxylic acid represented by the following formula (7) or its halide with the acyl imine compound having phenolic hydroxyl groups at both terminals, the dicarboxylic acid represented by the following formula (7) or the The above number average molecular weight can be adjusted by the equivalent ratio or the reaction time between the halide and the imine compound having phenolic hydroxyl groups at both ends. Alternatively, it may be used in an esterification reaction with an aromatic monocarboxylic acid represented by the following formula (8-1) or its halide and/or an aromatic monocarboxylic acid represented by the following formula (8-2) or its halide. Purification by GPC before or after the reaction. n in the above formula (1) can be adjusted similarly.

In the formula (5), X is the same base as X in the above formula (1).

In the formula (7), Y is the same base as Y in the above formula (1).

In the formula (8-1), R ¹ is the same base as R ¹ in the above formula (1), and in the formula (8-2), R ² is the same base as R ² in the above formula (1).

Examples of the acid dianhydride represented by the above formula (5) include 3,3'-oxydiphthalic dianhydride (3,3'-oxydiphthalic dianhydride) and 3,4'-oxydiphthalic dianhydride. Formic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride, 4,4' - Bis (3,4-dicarboxyphenoxy) diphenyl ether anhydride, p-phenylene bis (trimellitate anhydride), 4,4'-carbonyl diphthalic dianhydride, etc. Among them, 4,4'-oxydiphthalic dianhydride and 4,4'-(4,4'-isopropylidene diphenoxy base) diphthalic anhydride, more preferably 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride.

Examples of the amine phenol represented by the above formula (6) include 3-amine phenol, 4-amine phenol, and the like.

Examples of the dicarboxylic acid represented by the above formula (7) include terephthalic acid, isophthalic acid, 4,4'-oxybibenzoic acid, 2,7-naphthalenedicarboxylic acid, and the like. Among them, terephthalic acid and isophthalic acid are preferred.

Examples of the aromatic monocarboxylic acid represented by the above formula (8-1) and the aromatic monocarboxylic acid represented by the above formula (8-2) include 1-naphthoic acid, 2-naphthoic acid, 1-anthracenecarboxylic acid, and 2-naphthoic acid. -Anthracenecarboxylic acid, 9-anthracenecarboxylic acid, phenanthrenecarboxylic acid, pyrenecarboxylic acid, etc. Among them, 2-naphthoic acid is preferred.

A resin composition containing a curable resin and the polyfunctional active ester compound of the present invention is also one of the present invention. By containing the polyfunctional active ester compound of the present invention, the resin composition of the present invention makes the cured product excellent in heat resistance and dielectric properties. Therefore, the resin composition of the present invention can be suitably used to form an insulating layer in a multilayer printed wiring board.

In order to improve processability in an uncured state, the resin composition of the present invention may also contain other hardeners in addition to the polyfunctional active ester compound of the present invention within a range that does not hinder the purpose of the present invention. Examples of the above-mentioned other hardeners include phenol-based hardeners, mercaptan-based hardeners, amine-based hardeners, acid anhydride-based hardeners, cyanate ester-based hardeners, and other active agents other than the polyfunctional active ester compound of the present invention. Ester hardener, etc. Among these, active ester-based hardeners and cyanate ester-based hardeners other than the polyfunctional active ester compound of the present invention are preferred.

When only the multifunctional active ester compound of the present invention is used as the above-mentioned hardener, the content of the multifunctional active ester compound of the present invention is preferably 0.3 equivalents with respect to 1 equivalent of the curable resin, and the preferred upper limit is 2.0 equivalents. . When only the polyfunctional active ester compound of the present invention is used as the above-mentioned hardener, the resin composition obtained by having the content of the polyfunctional active ester compound of the present invention becomes more excellent in heat resistance and dielectric properties in this range. . When only the multifunctional active ester compound of the present invention is used as the above-mentioned hardener, a more preferable lower limit of the content of the multifunctional active ester compound of the present invention is 0.6 equivalents, and a more preferable upper limit is 1.5 equivalents. Moreover, when the polyfunctional active ester compound of the present invention is used in combination with other hardeners as the above-mentioned hardener, the content of the polyfunctional active ester compound of the present invention is preferably 0.05 equivalent relative to 1 equivalent of the curable resin. A preferred upper limit is 1.8 equivalents. When the multifunctional active ester compound of the present invention is used in combination with other hardeners as the above-mentioned hardener, the content of the multifunctional active ester compound of the present invention is within this range, and the resulting resin composition has excellent heat resistance and dielectric properties. Those with more excellent characteristics. When the multifunctional active ester compound of the present invention is used in combination with other hardeners as the above-mentioned hardener, a more preferable lower limit of the content of the multifunctional active ester compound of the present invention is 0.2 equivalents, and a more preferable upper limit is 1.2 equivalents. When the multifunctional active ester compound of the present invention and other hardeners are used together as the above-mentioned hardener, the preferred lower limit of the total content of the multifunctional active ester compound of the present invention and other hardeners relative to 1 equivalent of the curable resin is 0.3 equivalents, and the preferred upper limit is 2.0 equivalents.

The resin composition of the present invention contains curable resin. Examples of the curable resin include epoxy resin, cyanate resin, phenol resin, imide resin, maleimide resin, benzene resin, silicone resin, acrylic resin, fluororesin, etc. . Among them, the above-mentioned curable resin preferably contains at least one selected from the group consisting of epoxy resin, cyanate ester resin, phenol resin, imine resin, maleimide resin and benzodiazepine resin, and more preferably Preferably contains epoxy resin. The above-mentioned curable resins may be used alone or in combination of two or more types.

Examples of the epoxy resin include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, and 2,2'-diallyl Bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, sulfide Type epoxy resin, diphenyl ether type epoxy resin, sescyclopentadiene type epoxy resin, naphthalene type epoxy resin, quinoa type epoxy resin, naphthyl ether type epoxy resin, phenol novolak type epoxy Resin, o-cresol novolak type epoxy resin, secyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin, epoxypropylamine type epoxy Resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, epoxy propyl ester compound, etc.

The resin composition of the present invention preferably contains a hardening accelerator. By containing the above-mentioned hardening accelerator, the hardening time can be shortened and productivity can be improved.

Examples of the above-mentioned hardening accelerator include imidazole-based hardening accelerators, tertiary amine-based hardening accelerators, phosphine-based hardening accelerators, photobase generators, sulfonium salt-based hardening accelerators, and the like. Among them, from the viewpoint of storage stability and curability, imidazole-based hardening accelerators and phosphine-based hardening accelerators are preferred. The above-mentioned hardening accelerator can be used alone or in combination of two or more types.

The preferable lower limit of the content of the above-mentioned hardening accelerator is 0.01 parts by weight and the preferable upper limit is 10 parts by weight relative to 100 parts by weight of the above-mentioned curable resin. When the content of the above-mentioned curing accelerator is within this range, the effect of "shortening the curing time without deteriorating the adhesiveness of the obtained resin composition" becomes more excellent. A better lower limit of the content of the above-mentioned hardening accelerator is 0.03 parts by weight, a better upper limit is 4 parts by weight, a still better lower limit is 0.05 parts by weight, and a still better upper limit is 3 parts by weight.

The resin composition of the present invention preferably further contains an inorganic filler. By containing the above-mentioned inorganic filler, the resin composition of the present invention becomes more excellent in adhesiveness, workability, electrical properties, and heat resistance of the cured product.

The inorganic filler is preferably at least one of silica and alumina. By containing at least one of silica and alumina as the inorganic filler, the resin composition of the present invention becomes more excellent in adhesiveness, workability, electrical properties and heat resistance of the cured product. The above-mentioned inorganic filler is more preferably silica, and still more preferably fused silica.

Examples of inorganic fillers other than the above-mentioned silica and the above-mentioned alumina include barium sulfate, talc, clay, mica, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, silicon nitride, and glass powder. Glass glue, glass fiber, carbon fiber, inorganic ion exchanger, etc.

The above-mentioned inorganic fillers can be used alone or in combination of two or more kinds.

The preferred lower limit of the average particle size of the above-mentioned inorganic filler is 50 nm, and the preferred upper limit is 5 μm. When the average particle diameter of the above-mentioned inorganic filler is within this range, the resulting resin composition becomes more excellent in coating properties and processability. A more preferable lower limit of the average particle size of the above-mentioned inorganic filler is 75 nm, a more preferable upper limit is 3 μm, a still more preferable lower limit is 100 nm, and a more preferable upper limit is 2 μm. In addition, the average particle diameter of the above-mentioned inorganic filler or the flow regulator described below can be measured by, for example, using a particle size distribution measuring device to disperse the above-mentioned inorganic filler or flow regulator in a solvent (water, organic solvent, etc.). Examples of the particle size distribution measuring device include NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The preferred lower limit of the content of the above-mentioned inorganic filler in 100 parts by weight of the solid content of the resin composition of the present invention is 50 parts by weight, and the preferred upper limit is 85 parts by weight. When the content of the above-mentioned inorganic filler is within this range, the resulting resin composition becomes one that is more excellent in adhesiveness, processability, electrical properties, and heat resistance of the cured product. A more preferable lower limit of the above-mentioned inorganic filler content is 55 parts by weight, and a more preferable upper limit is 80 parts by weight. In addition, when the above-mentioned “solid content” uses a solvent described below, it means the total of the resin composition components excluding the solvent.

The resin composition of the present invention may also contain a flow regulator in order to improve the coatability and shape retention of the adherend in a short time. Examples of the flow regulator include fumed silica such as silicon thixotrope, layered silicate, and the like. The above-mentioned flow regulators can be used alone or in combination of two or more types. In addition, as the above-mentioned flow regulator, one having an average particle diameter of less than 50 nm is suitable.

The preferred lower limit of the content of the flow regulator is 0.1 parts by weight and the preferred upper limit is 100 parts by weight based on 100 parts by weight of the curable resin. When the content of the above-mentioned flow regulator is within this range, the effect of "improving the coatability and shape retention of the adherend in a short time" will be more excellent. A better lower limit of the flow regulator content is 0.5 parts by weight, and a better upper limit is 50 parts by weight.

The resin composition of the present invention may also contain an organic filler for the purpose of relaxing stress, imparting toughness, etc. Examples of the organic filler include polysilicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamide imine particles, polyimide particles, and benzene guanidine particles. And these core-shell particles, etc. Among them, polyamide particles, polyamide imine particles, and polyimide particles are preferred. The above-mentioned organic fillers can be used alone or in combination of two or more kinds.

The preferred upper limit of the content of the above-mentioned organic filler in 100 parts by weight of the solid content of the resin composition of the present invention is 300 parts by weight. When the content of the above-mentioned organic filler is within this range, the resulting cured product of the resin composition becomes one that is more excellent in toughness and the like while maintaining excellent adhesion and the like. A better upper limit of the content of the above-mentioned organic filler is 200 parts by weight.

The resin composition of the present invention may also contain a flame retardant. Examples of the flame retardant include diaspore-type aluminum hydroxide, aluminum hydroxide, magnesium hydroxide, halogen-based compounds, phosphorus-based compounds, nitrogen compounds, and the like. Among them, diaspore-type aluminum hydroxide is preferred. The above-mentioned flame retardants can be used alone or in combination of two or more types.

The content of the flame retardant is preferably 2 parts by weight and 300 parts by weight relative to 100 parts by weight of the curable resin. When the content of the flame retardant is within this range, the resulting resin composition has excellent flame retardancy while maintaining excellent adhesion and the like. A better lower limit of the flame retardant content is 5 parts by weight, and a better upper limit is 250 parts by weight.

The resin composition of the present invention preferably contains a thermoplastic resin. By using the above-mentioned thermoplastic resin, the resin composition of the present invention has excellent flow characteristics, electrical characteristics, and bending resistance after curing.

Examples of the thermoplastic resin include polyamide resin, phenoxy resin, polyamide resin, polyamide imine resin, polyvinyl acetal resin, and the like. Among them, polyimide resin and phenoxy resin are preferred because they can effectively reduce the dielectric loss tangent regardless of the hardening environment and can adjust the melt viscosity. The above-mentioned thermoplastic resins can be used alone or in combination of two or more types.

The preferred lower limit of the number average molecular weight of the thermoplastic resin is 2,000, and the preferred upper limit is 100,000. When the number average molecular weight of the thermoplastic resin is within this range, the resulting resin composition has better flow characteristics, electrical characteristics, and bending resistance after curing. A more preferable lower limit of the number average molecular weight of the thermoplastic resin is 5,000, and a more preferable upper limit is 50,000.

The content of the thermoplastic resin is preferably 0.5 parts by weight and 50 parts by weight relative to 100 parts by weight of the curable resin. When the content of the thermoplastic resin is 0.5 parts by weight or more, the resulting resin composition has better flow characteristics or bending resistance after curing. When the content of the thermoplastic resin is 50 parts by weight or less, the obtained cured product has better heat resistance. A more preferable lower limit of the thermoplastic resin content is 1 part by weight, and a more preferable upper limit is 30 parts by weight.

The resin composition of the present invention may also contain a solvent. By using the above-mentioned solvents, the viscosity of the resin material can be controlled within a more suitable range, and the coating properties of the resin material can be improved. In addition, the above-mentioned solvent can also be used to obtain a slurry containing the above-mentioned inorganic filler. The above-mentioned solvents can be used alone or in combination of two or more kinds.

Examples of the solvent include acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, and 2-acetyl. Oxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N,N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidinone, n-hexane , cyclohexane, cyclohexanone and light oil as a mixture, etc. Among them, from the viewpoint of coating properties or storage stability, the boiling point of the solvent is preferably 200°C or lower, more preferably 180°C or lower. In addition, the above-mentioned "boiling point" means a value measured under conditions of 101 kPa, or a value converted to 101 kPa using a boiling point conversion chart or the like.

The preferred lower limit of the above-mentioned solvent content in 100 parts by weight of the resin composition of the present invention is 10 parts by weight, and the preferred upper limit is 60 parts by weight. When the content of the above-mentioned solvent is within this range, the resin composition of the present invention becomes more excellent in coating properties and the like. A more preferable lower limit of the above solvent content is 20 parts by weight, and a more preferable upper limit is 40 parts by weight.

The resin composition of the present invention may also contain a reactive diluent within a range that does not hinder the object of the present invention. As the reactive diluent, one having two or more reactive functional groups per molecule is preferred from the viewpoint of bonding reliability.

The resin composition of the present invention may further contain additives such as coupling agents, dispersants, storage stabilizers, anti-flooding agents, fluxes, and leveling agents.

An example of a method for producing the resin composition of the present invention is a method of mixing a curable resin, a curing agent, an inorganic filler or a solvent if necessary using a mixer. Examples of the above-mentioned mixer include a homogenizer, a multi-purpose mixer, a Banbury mixer, and a kneader.

By coating the resin composition of the present invention on a base film and drying it, a resin composition film composed of the resin composition of the present invention can be obtained, and the resin composition film can be cured to obtain a cured product. The cured product of the resin composition of the present invention is also one of the present invention.

When a biphenyl-type epoxy resin is included as the above-mentioned curable resin, the preferred lower limit of the linear expansion coefficient of the cured product of the resin composition of the present invention in the temperature range of 25°C to 150°C is 3 ppm/°C. The upper limit is 60ppm/℃. The cured product of the resin composition of the present invention has better heat resistance. The better lower limit of the linear expansion coefficient is 5ppm/℃, the better upper limit is 40ppm/℃, the still better upper limit is 28ppm/℃, and the more preferable upper limit is 25ppm/℃. In addition, the above-mentioned "linear expansion coefficient" in this specification means a value measured by the thermomechanical analysis (TMA) method under the conditions of a temperature rise rate of 5°C/min and a force of 33N. In addition, the cured product used for the measurement of the linear expansion coefficient can be obtained by heating the above-mentioned resin composition film having a thickness of approximately 40 μm at 190° C. for 90 minutes, for example.

When a biphenyl-type epoxy resin is contained as the above-mentioned curable resin, the preferred upper limit of the dielectric loss tangent of the cured product of the resin composition of the present invention at 23° C. is 0.015. Since the dielectric loss tangent of the cured product at 23° C. is 0.015 or less, the resin composition of the present invention can be suitably used as an interlayer insulating material for multilayer printed wiring boards and the like. A more preferable upper limit of the dielectric loss tangent of the above-mentioned hardened material at 23°C is 0.01, a still more preferable upper limit is 0.0035, and a particularly preferable upper limit is 0.003. In addition, the above-mentioned "dielectric loss tangent" is a value measured using a dielectric coefficient measuring device and a network analyzer under the conditions of 5 GHz. In addition, the cured product for measuring the "dielectric loss tangent" can be obtained by heating the above resin composition film with a thickness of 40 μm to about 200 μm at 190° C. for 90 minutes.

The resin composition of the present invention can be used in a wide range of applications, and is particularly suitable for electronic material applications requiring high heat resistance. For example, it can be used as a die attach agent for aviation and automotive electrical control units (ECUs) or power components using SiC and GaN. In addition, it can also be used, for example, in adhesives for power overlay packages, adhesives for printed wiring boards, adhesives for covering flexible printed circuit boards, copper-clad laminates, adhesives for semiconductor bonding, and interlayer insulating materials. , prepreg, sealant for LED, adhesive for structural materials, etc. Among them, the resin composition of the present invention is suitable for use in build-up films because the cured product has low dielectric coefficient, low dielectric loss tangent, and excellent dielectric properties. The build-up film using the resin composition of the present invention is also one of the present invention. [Effects of the invention]

According to the present invention, it is possible to provide a polyfunctional active ester compound capable of obtaining a resin composition having excellent heat resistance and dielectric properties after curing. Furthermore, according to the present invention, it is possible to provide a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a build-up film using the resin composition.

The following examples are disclosed to further illustrate the present invention in detail, but the present invention is not limited to these examples.

(Synthesis Example 1 (Preparation of Polyfunctional Active Ester Compound A)) 130.96 parts by weight of 3-amine phenol was dissolved in 1400 mL of N-methylpyrrolidone. 208.20 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride was added to the obtained solution, and the mixture was stirred for 2 hours at 25°C to react, thereby obtaining amide Solution of acid compound. The obtained amide compound was added to 8400 mL of 1 mol/L acetic acid, and the precipitate was recovered. By heating the obtained precipitate at 300° C. for 2 hours, a acyl imine compound having phenolic hydroxyl groups at both terminals was obtained. 8.43 parts by weight of the obtained imine compound having phenolic hydroxyl groups at both ends and 3.64 parts by weight of triethylamine were dissolved in 60 mL of tetrahydrofuran. To the obtained solution, 1.22 parts by weight of paraphthalene chloride was added, and after stirring at 25°C for 4 hours, 2.63 parts by weight of 2-naphthalene carbonyl chloride was added, and the mixture was further stirred at 25°C for 18 hours to esterify. reaction. As p-phthaloyl chloride and 2-naphthoyl chloride, reagents manufactured by Tokyo Chemical Industry Co., Ltd. were used. Then, tetrahydrofuran was removed, and the remaining solid was washed with pure water, thereby obtaining polyfunctional active ester compound A. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound A contained the compound represented by the above formula (4). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound A was 1,900. In addition, the number average molecular weight was determined by GPC analysis (solvent: tetrahydrofuran, column: JAIGEL-2H-A, flow rate: 1.0 mL/min) in the form of polystyrene-converted number average molecular weight.

(Synthesis Example 2 (Preparation of Polyfunctional Active Ester Compound B)) The polyfunctional active ester compound B was obtained in the same manner as Synthesis Example 1, except that the blending amount of phthalyl chloride was changed to 1.62 parts by weight. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound B contained a compound represented by the following formula (9). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound B was 2,700.

(Synthetic Example 3 (Preparation of Polyfunctional Active Ester Compound C)) Except for changing 1.22 parts by weight of phthaloyl chloride into 1.22 parts by weight of isophthaloyl chloride, the polyfunctional ester compound was obtained in the same manner as in Synthesis Example 1. Functional active ester compound C. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound C contains a compound represented by the following formula (10). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound C was 1,900.

(Synthesis Example 4 (Preparation of Polyfunctional Active Ester Compound D)) The polyfunctional active ester compound D was obtained in the same manner as Synthesis Example 3, except that the blending amount of isophthalyl chloride was changed to 1.62 parts by weight. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound D contained a compound represented by the following formula (11). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound D was 2,700.

(Synthesis Example 5 (Preparation of Polyfunctional Active Ester Compound E)) Except for changing 208.20 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride to 4, 124.09 parts by weight of 4'-oxydiphthalic dianhydride, and the usage amount of the imine compound having phenolic hydroxyl groups at both ends was changed from 8.43 parts by weight to 5.91 parts by weight, and the rest were the same as in Synthesis Example 1 Polyfunctional active ester compound E was obtained in the same manner. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound E contained a compound represented by the following formula (12). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound E was 1,500.

(Synthesis Example 6 (Preparation of Polyfunctional Active Ester Compound F)) The polyfunctional active ester compound F was obtained in the same manner as Synthesis Example 5, except that the blending amount of phthalyl chloride was changed to 1.62 parts by weight. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound F contained a compound represented by the following formula (13). Moreover, the number average molecular weight of the obtained polyfunctional active ester compound F was 2100.

(Synthesis Example 7 (Preparation of Polyfunctional Active Ester Compound G)) The polyfunctional active ester compound G was obtained in the same manner as Synthesis Example 1 except for the following changes. That is, 208.20 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic dianhydride was changed to 124.09 parts by weight of 4,4'-oxydiphthalic dianhydride. parts by weight, the usage amount of the imine compound having phenolic hydroxyl groups at both ends was 5.91 parts by weight, and 1.22 parts by weight of paraphthalate chloride was changed to 1.22 parts by weight of isophthalate chloride. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound G contained a compound represented by the following formula (14). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound G was 1,500.

(Synthesis Example 8 (Preparation of Polyfunctional Active Ester Compound H)) The polyfunctional active ester compound H was obtained in the same manner as in Synthesis Example 7, except that the blending amount of isophthaloyl chloride was changed to 1.62 parts by weight. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound H contains a compound represented by the following formula (15). Moreover, the number average molecular weight of the obtained polyfunctional active ester compound H was 2100.

(Synthetic Example 9 (Preparation of Polyfunctional Active Ester Compound I)) Except for changing 2.63 parts by weight of 2-naphthoyl chloride into 1.94 parts by weight of benzoyl chloride, the polyfunctional active compound was obtained in the same manner as in Synthetic Example 1. Ester compound I. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound I contained a compound represented by the following formula (16). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound I was 1,800.

(Synthesis Example 10 (Preparation of Polyfunctional Active Ester Compound J)) The polyfunctional active ester compound J was obtained in the same manner as in Synthesis Example 9, except that the blending amount of phthalochloride was changed to 1.62 parts by weight. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound J contained a compound represented by the following formula (17). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound J was 2,600.

(Synthesis Example 11 (Preparation of Polyfunctional Active Ester Compound K)) In addition to changing 1.22 parts by weight of p-phthalate chloride to 1.22 parts by weight of isophthaloyl chloride, 2.63 parts by weight of 2-naphthyl chloride was changed to benzyl chloride Except for 1.94 parts by weight, the polyfunctional active ester compound K was obtained in the same manner as in Synthesis Example 1. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound K contains a compound represented by the following formula (18). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound K was 1,800.

(Synthesis Example 12 (Preparation of Polyfunctional Active Ester Compound L)) The polyfunctional active ester compound L was obtained in the same manner as in Synthesis Example 11, except that the blending amount of isophthaloyl chloride was changed to 1.62 parts by weight. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound L contained a compound represented by the following formula (19). Furthermore, the number average molecular weight of the obtained polyfunctional active ester compound L was 2,600.

(Synthesis Example 13 (Preparation of Polyfunctional Active Ester Compound M)) 130.96 parts by weight of 3-amine phenol was dissolved in 1400 mL of N-methylpyrrolidone. 208.20 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride was added to the obtained solution, and the mixture was stirred for 2 hours at 25°C to react, thereby obtaining amide Solution of acid compound. The obtained amide compound was added to 8400 mL of 1 mol/L acetic acid, and the precipitate was recovered. By heating the obtained precipitate at 300° C. for 2 hours, a acyl imine compound having phenolic hydroxyl groups at both terminals was obtained. 8.43 parts by weight of the obtained acyl imine compound and 4.86 parts by weight of triethylamine were dissolved in 130 mL of tetrahydrofuran. 4.80 parts by weight of 2-naphthoyl chloride was added to the obtained solution, and the mixture was stirred at 25° C. for 4 hours to perform an esterification reaction. Then, tetrahydrofuran was removed under reduced pressure to obtain the polyfunctional active ester compound M. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound M contained a compound represented by the following formula (20).

(Synthesis Example 14 (Preparation of Polyfunctional Active Ester Compound N)) Using a container equipped with a stirrer, a reflux cooler, and a Dean-Stark water separator, 21.8 parts by weight of 3-amine phenol was added Dissolve in 100mL of N-methylpyrrolidone. 52.0 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride was added to the obtained solution, and the mixture was stirred at 25° C. for 4 hours to react. After adding 100 mL of toluene to the obtained solution, the solution was refluxed at 150° C. for 4 hours until water no longer was produced. After the reaction, toluene was removed from the obtained solution using an evaporator, the obtained solution was dropped into 800 mL of pure water, and the precipitate was filtered off. Further, 70.3 parts by weight of the obtained precipitate and 20.2 parts by weight of triethylamine were dissolved in 200 mL of N-methyl-2-pyrrolidinone. 28.1 parts by weight of benzoyl chloride was added to the obtained solution, and the mixture was stirred at 25° C. for 4 hours to react. After the reaction, the obtained solution was dropped into 800 mL of pure water, and the precipitate was filtered off, followed by vacuum drying to obtain the polyfunctional active ester compound N. In addition, it was confirmed by ¹ H-NMR, GPC and FT-IR analysis that the polyfunctional active ester compound N was not represented by the above formula (1).

(Examples 1 to 12, Comparative Examples 1 to 3) Cyclohexanone as a solvent was added to each material at the blending ratio described in Tables 1 and 2, and the mixture was stirred at 1200 rpm for 4 hours using a mixer to obtain a resin composition. In addition, in the compositions of Tables 1 and 2, the solid content excluding the solvent is described. The obtained resin composition was applied to the release-processed surface of a PET film with a thickness of 25 μm using an applicator. As the PET film, XG284 (manufactured by Toray Industries) was used. Then, it was dried in a gear oven at 100°C for 2.5 minutes to evaporate the solvent. In this way, an unhardened laminated film having a PET film and a resin composition layer on the PET film was obtained, the thickness of the resin composition layer was 40 μm, and the residual amount of the solvent was 1.0% by weight or more and 7.0% by weight or less.

＜Evaluation＞ The following evaluations were performed on each of the uncured laminated films obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(heat resistance) Each of the uncured laminated films obtained in Examples and Comparative Examples was heated at 190° C. for 90 minutes, and then the base PET film was peeled off to obtain a cured product. Using a thermomechanical analysis device on the obtained hardened material, the linear expansion coefficient in the temperature range of 25°C to 150°C was measured under the conditions of a temperature rise rate of 5°C/min and a force of 33N. As a thermomechanical analysis device, TMA7100 (manufactured by Hitachi High-Tech Scientific Corporation) was used. The case where the linear expansion coefficient is 25ppm/℃ or less is regarded as "○", the case where it exceeds 25ppm/℃ but is below 28ppm/℃ is regarded as "△", the case where it exceeds 28ppm/℃ is regarded as "×", and Heat resistance was evaluated.

(dielectric properties) Each of the uncured laminated films obtained in Examples and Comparative Examples was heated at 190° C. for 90 minutes, and then the base PET film was peeled off to obtain a cured product. The obtained hardened material was cut into a size of 2 mm in width and 100 mm in length. Use a cavity resonance perturbation method dielectric coefficient measuring device and a network analyzer to measure the dielectric loss tangent of the cut hardened material under the conditions of 23°C and 5GHz using the cavity resonance method. As the cavity resonance perturbation method dielectric coefficient measuring device, CP521 (manufactured by Kanto Electronics Application Development Co., Ltd.) was used, and as the network analyzer, N5224A PNA (manufactured by Keysight Technologies, Inc.) was used. The case where the dielectric loss tangent is 0.0025 or less is designated as "◎", the case where it exceeds 0.0025 but is below 0.003 is designated as "○", the case where it exceeds 0.003 but is below 0.0035 is designated as "△", and the case where it exceeds 0.0035 is designated as "△" The situation will be "×" and the dielectric properties are evaluated.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 12 Composition (parts by weight) hardening resin Biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "NC-3000", number average molecular weight 800) 100 100 100 100 100 100 100 100 100 100 100 100 Hardener Multifunctional active ester compound of the present invention Ester compound A 134 - - - - - - - - - - - Ester compound B - 129 - - - - - - - - - - Ester compound C - - 134 - - - - - - - - - Ester compound D - - - 129 - - - - - - - - Ester compound E - - - - 103 - - - - - - - Ester compound F - - - - - 99 - - - - - - Ester compound G - - - - - - 103 - - - - - Ester compound H - - - - - - - 99 - - - - Ester compound I - - - - - - - - 126 - - - Ester compound J - - - - - - - - - 124 - - Ester compound K - - - - - - - - - - 126 - Ester compound L - - - - - - - - - - - 124 hardening accelerator N,N-Dimethyl-4-aminepyridine 5 5 5 5 5 5 5 5 5 5 5 5 thermoplastic resin Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX6954BH30") 20 20 20 20 20 20 20 20 20 20 20 20 Inorganic filler Silica-containing slurry (manufactured by Yaduma Technology Co., Ltd., "SC4050-HOA") 286 281 286 282 532 523 532 524 586 581 586 582 Evaluation heat resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Dielectric properties ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

[Table 2] Comparative example 1 2 3 Composition (parts by weight) hardening resin Biphenyl-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "NC-3000", number average molecular weight 800) 100 100 100 Hardener Other active ester hardeners Ester compound M 147 - - Ester compound N - 146 - EXB-9416 (made by DIC Corporation) - - 96 hardening accelerator N,N-Dimethyl-4-aminepyridine 5 5 5 thermoplastic resin Phenoxy resin (manufactured by Mitsubishi Chemical Corporation, "YX6954BH30") 20 20 20 Inorganic filler Silica-containing slurry (manufactured by Yaduma Technology Co., Ltd., "SC4050-HOA") 635 632 516 Evaluation heat resistance △ × △ Dielectric properties ○ ○ ○ [Industrial availability]

According to the present invention, it is possible to provide a polyfunctional active ester compound capable of obtaining a resin composition having excellent heat resistance and dielectric properties after curing. Furthermore, according to the present invention, it is possible to provide a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a build-up film using the resin composition.

without

without

Claims (10)

A multifunctional active ester compound represented by the following formula (1),

In formula (1), R ¹ and R ² may each be the same or different, and may be an aryl group that may be substituted. X is each independently an oxygen atom or a divalent group, Y is a divalent organic group, n is an integer above 1. The polyfunctional active ester compound of claim 1, wherein n in the formula (1) is 1 or more and 5 or less. For example, the polyfunctional active ester compound of claim 1 or 2 has a number average molecular weight of not less than 1,300 and not more than 5,500. The polyfunctional active ester compound of claim 1 or 2, wherein Y in the formula (1) is 1,3-phenylene group or 1,4-phenylene group. The polyfunctional active ester compound of claim 1 or 2, wherein R ¹ and R ² in the formula (1) are groups represented by the following formula (2),

In the formula (2), R ³ is each independently a hydrogen atom or an aliphatic group, and * is a bonding position. The polyfunctional active ester compound of claim 1 or 2, wherein X in the formula (1) is an oxygen atom or a group represented by the following formula (3),

In formula (3), * is the bonding position. A resin composition containing a curable resin and the multifunctional active ester compound of claim 1, 2, 3, 4, 5 or 6. The resin composition of claim 7 further contains an inorganic filler. A hardened product of the resin composition of claim 7 or 8. A build-up film made of the resin composition of claim 7 or 8.