Curable composition

Abstract

[Problem] To provide a curable composition with which a cured product having excellent electrical properties (low relative dielectric constant, low dielectric tangent, etc.) and moisture resistance, as well as mechanical properties, insulating properties, etc. can be formed, and which is useful for electronic component device usages such as encapsulants for semiconductor devices, build-up films, or underfill materials, and has excellent handleability and permeability into narrow gaps. [Solution] A curable composition including: an epoxy resin; a curing agent having an amino group; and hollow silica particles surface-treated with a silane coupling agent having an amino group or a group capable of undergoing an addition reaction with an amino group, wherein the hollow silica particles have an average particle diameter (D50) of 0.5 μm or more.

Description

curable composition

[0001] This invention relates to a curable composition. More specifically, this invention relates to a curable composition comprising an epoxy resin, a curing agent, and inorganic particles.

[0002] In recent years, to cope with the miniaturization of electronic devices, the acceleration of signals, and the increase in wiring density, there has been a demand for high-performance insulating materials (low dielectric constant, low dielectric loss tangent, low thermal expansion, etc.) such as sealing resin compositions, build-up substrates, adhesive films, prepregs, and printed circuit boards for communication equipment, and various studies have been conducted. Patent Document 1 proposes a resin composition containing epoxy resin, a curing agent, hollow silica, and fused silica, in which the content of hollow silica and the total content of hollow silica and fused silica are within a predetermined range, as a material for adhesive films, prepregs, etc., for electronic component applications. Furthermore, flip-chip bonding is used as a semiconductor chip mounting method that can cope with the miniaturization of electronic devices, the acceleration of signals, and the increase in wiring density. In flip-chip bonding, the gap between the semiconductor chip and the substrate is sealed with a material called underfill. Patent Document 2 proposes a liquid resin composition containing, in a specific ratio, solid silica particles with a particle size on the order of nanometers, surface-treated with epoxy resin, a curing agent, and a silane coupling agent, and solid silica particles with a particle size on the order of micrometers, as a material for electronic component applications.

[0003] Japanese Patent Publication No. 2013-173841 Japanese Patent Publication No. 2020-066695

[0004] In these resin compositions, the physical properties of the epoxy resin form the basis for various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, and mechanical properties. On the other hand, when increasing the content of inorganic fillers to improve electrical properties (relative permittivity, low dielectric loss tangent, etc.) while ensuring the uniformity of the resulting cured product, the dispersibility of the constituent components tends to decrease, and the effect is not fully obtained. Even in the resin compositions of Patent Document 1 or 2, there is still room for improvement in order to obtain a composition that provides physical properties such as electrical properties based on silica fillers, and is also capable of handling narrow gaps, and is excellent in fluidity, filling ability, moldability, temperature cycle resistance, and moisture resistance. The present inventors focused on the physical properties of the three components of such resin compositions: epoxy resin, curing agent, and silica particles, and investigated the behavior between the components in detail. As a result, they found that a composition containing a specific curing agent and hollow silica of a predetermined particle size, surface-treated with a specific coupling agent, can improve the dispersion state of silica particles in the composition, making it easier to handle and suppressing viscosity increase of the composition. We discovered that such compositions can form cured products (including molded products such as films) with excellent electrical properties (low dielectric constant, low dielectric loss tangent, etc.) and moisture resistance, leading to the present invention. The object of the present invention is to provide a curable composition that can form cured products with excellent electrical properties (low dielectric constant, low dielectric loss tangent, etc.) and moisture resistance, as well as mechanical properties and insulating properties, and is useful for electronic component devices such as encapsulants, build-up films, or underfill materials for semiconductor devices, and is excellent in handling and penetration into narrow gaps.

[0005] The present invention has the following embodiments: [1] A curable composition comprising an epoxy resin, a curing agent having an amino group, and hollow silica particles surface-treated with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group, wherein the average particle diameter (D50) of the hollow silica particles is 0.5 μm or more. [2] The curable composition of [1], wherein the curing agent is an aromatic amine compound. [3] The curable composition of [1] or [2], wherein the active hydrogen equivalent of the curing agent is 40 to 80 g / mol. [4] The curable composition of any of [1] to [3], wherein the silane coupling agent is a silane coupling agent having an amino group. [5] The curable composition of any of [1] to [4], wherein the silane coupling agent is a silane coupling agent having an epoxy group or a methacrylicloyloxy group. [6] The curable composition of any of [1] to [5] further comprising solid silica particles. [7] The curable composition of [6], wherein the solid silica particles are hollow silica particles surface-treated with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group. [8] The curable composition of [7], wherein the silane coupling agent is a silane coupling agent having an amino group, or a silane coupling agent having an epoxy group or a methacrylicloyloxy group. [9] The curable composition of [8], wherein the average particle diameter of the solid silica particles is 0.01 to 10 μm.

[10] The curable composition of [8] or [9], wherein the ratio of the average particle diameter (D50) of the hollow silica particles to the average particle diameter (D50) of the solid silica particles is 0.1 to 10.

[11] The curable composition of any one of [8] to

[10] , wherein the ratio of the hollow silica particles to the total amount of the solid silica particles and the hollow silica particles is 5% by volume or more.

[12] A curable composition according to any one of [8] to

[11] , wherein the total content of solid silica particles and hollow silica particles relative to the entire curable composition is 50% by volume or more.

[13] A cured product of any one of the curable compositions according to [1] to

[12] .

[14] A curable composition according to any one of [1] to

[12] for use in electronic component devices.

[15] A curable composition according to any one of [1] to

[12] for use as a encapsulant, build-up film, or underfill material for semiconductor devices.

[0006] According to the present invention, it is possible to form a curable product that has excellent electrical properties (low dielectric constant, low dielectric loss tangent, etc.) and moisture resistance, as well as mechanical properties and insulating properties, and provides a curable composition that is easy to handle and penetrates into narrow gaps.

[0007] In this specification, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. Furthermore, in numerical ranges described in this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages.

[0008] The present invention relates to a curable composition (hereinafter also referred to as "this composition") comprising an epoxy resin, a curing agent having an amino group, and hollow silica particles surface-treated with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group, wherein the average particle diameter (D50) of the hollow silica particles is 0.5 μm or more.

[0009] This composition can form a cured product with excellent electrical properties (low dielectric constant, low dielectric loss tangent, etc.) and moisture resistance, as well as mechanical properties, insulation, low linear expansion, and adhesiveness. It also exhibits excellent handling and penetration into narrow gaps. This composition can be effectively used in various applications that take advantage of these properties, and can be effectively used in electronic component devices such as encapsulants, build-up films, or underfill materials for semiconductor devices. The reason why this composition can form a cured product with excellent handling and penetration into narrow gaps, as well as excellent electrical properties (low dielectric constant, low dielectric loss tangent, etc.), moisture resistance, mechanical properties, insulation, low linear expansion, and adhesiveness, is not entirely clear, but it is thought to be as follows.

[0010] Silica particles whose surfaces are treated with a silane coupling agent generally exhibit improved compatibility with epoxy resins, resulting in a lower viscosity and improved narrow gap properties and handling characteristics in the resulting composition. However, the reaction of the epoxy resin due to the action of the curing agent can be considered a sequential reaction and is susceptible to the influence of the properties of the curing agent and the chemical and physical properties of the silica particles. In particular, when the silica particles are hollow silica particles with a particle size above a certain level, they are susceptible to the influence of the physical properties of the particles themselves, such as specific gravity and specific surface area. In a curable composition containing epoxy resin, a curing agent, and hollow silica particles of a predetermined particle size, the curing agent is a curing agent having an amino group, and the hollow silica particles are surface-treated with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group. It is presumed that in the reaction of the epoxy resin accompanying the action of the curing agent having an amino group, the surface-treated hollow silica particles react with the epoxy resin or the curing agent having an amino group, hybridizing with the epoxy resin and being highly incorporated into the cured product. Therefore, it is believed that this composition not only has excellent fluidity and penetration into narrow gaps, but also produces a cured product with good electrical properties and moisture resistance, low thermal expansion coefficient and elastic modulus, excellent stress suppression effect inside the package, and excellent adhesive strength.

[0011] In this composition, the epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. The epoxy resin may be solid or liquid at room temperature (25°C), but it is more preferable that it be liquid at room temperature from the viewpoint of improving the handling (pot life) and filling properties of this composition. The viscosity of the liquid epoxy resin is preferably 0.0001 to 10 Pa·s when measured at 25°C using an E-type viscometer. The epoxy equivalent of the epoxy resin is preferably 40 to 200 g / eq. When the epoxy equivalent is within the above range, the molecular size is relatively compact, and it is presumed that it reacts closely with certain silane coupling agents described later to form a loose (highly flexible) network, which easily buffers the cracking of hollow silica particles. The epoxy equivalent in this specification is the mass of resin per epoxy group (g / eq) and is determined according to JIS K 7236. Specifically, the measurement can be performed by weighing 0.2 g of epoxy resin, dissolving it in 10 ml of chloroform, adding 20 ml of glacial acetic acid and 10 ml of tetraethylammonium bromide acetic acid solution, and then titrating with a 0.1 mol / L perchloric acid acetic acid solution.

[0012] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, adamantane type epoxy resin, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, triglycidyl isocyanurate, and the like. Epoxy resins may be used individually or in combination of two or more types.

[0013] In this composition, the active hydrogen equivalent of the curing agent having an amino group is preferably 40 to 80 g / mol. When the active hydrogen equivalent of the curing agent having an amino group is within the above range, the molecular size is relatively compact, and it is presumed that it reacts closely with certain silane coupling agents described later to form a loose and highly flexible network, which facilitates buffering of cracking of hollow silica particles. The curing agent having an amino group is preferably an amine-based curing agent, and more preferably an aromatic amine compound having a primary or secondary amino group. Examples of such aromatic amine compounds include bisanilines such as 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine; diaminobenzenes such as 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, and dimethylthiotoluenediamine; and 3,3'-diethyl-4,4'-diaminodiphenylmethane and 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane. These aromatic amine compounds may be solid or liquid at 25°C, but from the viewpoint of improving the fluidity of the composition, it is preferable that they be liquid at 25°C. In particular, it is preferable that the curing agent having an amino group is a bisaniline or a diaminobenzene, and it is more preferable that both bisanilines and diaminobenzenes are included as the curing agent having an amino group. In this case, there are no particular restrictions on the content range of bisanilines and diaminobenzenes in the curing agent, but from the viewpoint of better exhibiting the surfactant effect of the curing agent, it is preferable that the content of bisanilines be less than or equal to the content of diaminobenzenes.

[0014] In this specification, "bisanilines" refers to compounds in which multiple structural units (aniline units) are linked together, with one of the six carbon atoms forming a benzene ring directly bonded to a primary or secondary amino group. The amino groups in bisanilines are far apart, and it is presumed that the cured products are relatively less likely to exhibit properties similar to those of the surfactants described above. In this specification, "diaminobenzenes" refers to compounds having a structure in which two of the six carbon atoms forming a benzene ring are directly bonded to a primary or secondary amino group. The amino groups in diaminobenzenes are closer together than in bisanilines, and it is presumed that the cured products are relatively more likely to exhibit properties similar to those of the surfactants described above.

[0015] Commercial curing agents containing amino groups may be used. Examples of amine curing agents containing bisanilines include "KAYAHARD® A-A" (trade name, active hydrogen equivalent 64 g / mol) manufactured by Nippon Kayaku Co., Ltd. Examples of amine curing agents containing diaminobenzenes include "jER® Cure WA" (trade name, active hydrogen equivalent 45 g / mol) manufactured by Mitsubishi Chemical Corporation and "EH-105L" (trade name, active hydrogen equivalent 54 g / mol) manufactured by ADEKA Corporation. The curing agent in this composition may further contain other curing agents such as acid anhydride curing agents and phenolic curing agents, which are different from the above-mentioned curing agents containing amino groups, as long as they do not impair the effects of the present invention.

[0016] Furthermore, the equivalent ratio of the epoxy resin to the curing agent having amino groups in this composition (number of functional groups in the curing agent having amino groups / number of functional groups in the epoxy resin) is preferably 1.5 to 2.0, more preferably 0.6 to 1.3, from the viewpoint of minimizing the amount of unreacted material in each, and even more preferably 0.8 to 1.2 from the viewpoint of curability and reliability.

[0017] The hollow silica particles in this composition have a shell layer (solid film) containing silica, and have a space inside the shell layer. The presence of a space inside the shell layer of a hollow silica particle can be confirmed by transmission electron microscopy (TEM) or scanning electron microscopy (SEM) observation. In the case of SEM observation, the hollowness can be confirmed by observing a broken particle with a partial opening. Spherical particles with a space inside, which can be confirmed by TEM or SEM observation, are defined as "primary particles." Note that, due to the firing and drying processes during manufacturing, the primary particles are partially bonded together, so hollow silica particles are often aggregates of secondary particles formed by the aggregation of primary particles. Furthermore, "having a space inside the shell layer" means that when observing the cross-section of a single primary particle, the shell layer surrounds a single space, resulting in a hollow state. In other words, one hollow particle has one large space and a shell layer surrounding it. If the hollow silica particles have a structure in which there is a space within the shell, more space can be secured in the composition containing the particles, and the dielectric constant can be lowered, so this composition can be suitably used in electronic component devices.

[0018] The specific gravity of hollow silica particles is 0.3 g / cm³. ３ 1.00g / cm or more ３ Less than 0.4-0.8 g / cm³ ３ It is more preferable that this is the case. In this specification, the "specific gravity" of hollow silica particles refers to the density of the particles determined by density measurement using a dry pycnometer with argon gas (hereinafter also referred to as "Ar density"). When the Ar density is within the above range, not only is the above-described mechanism of action more likely to occur, but the dielectric constant of the cured product of this composition is also easier to reduce.

[0019] Furthermore, the density of the hollow silica particles, as determined by density measurement using a dry pycnometer with helium gas (hereinafter also referred to as He density), is 2.00 to 2.35 g / cm³. ３This is preferable. Since helium gas permeates through fine voids, the He density can also be positioned as the density corresponding to the true density of the silica portion of silica particles that have internal space. When the He density is within the above range, the amount of silanol remaining in the hollow silica particles decreases, making it easier to reduce the dielectric loss tangent.

[0020] The specific gravity (Ar density) of hollow silica particles can be adjusted by controlling the primary particle size and shell thickness. In a sample of hollow silica particles, the proportion of perfectly hollow particles (hollow particle ratio) that have an internal space without damage to the shell layer is determined by the amount of raw material used. A higher hollow particle ratio results in a lower apparent density of the hollow silica sample, while a lower hollow particle ratio results in a higher apparent density. Using this, assuming a 100% yield, the hollow particle ratio can be determined from the theoretical density obtained from the amount of raw material used and the apparent density measured with a dry pycnometer. In this case, a hollow particle ratio of 90% or more is preferable, and 95% or more is more preferable. Furthermore, a hollow particle ratio of 100% or less is preferable.

[0021] Furthermore, the hollow particle ratio can also be determined from the weight change during heat treatment using the filtration cake before the oil core is removed when manufacturing hollow silica particles. When the filtration cake is loosened and dried overnight, the oil components in the broken particles volatilize, while the oil components in the complete hollow particles are retained. The weight change during heat treatment can be calculated from the amount of raw material used for cases where all the added oil components volatilize (0% hollow particle ratio) and cases where all of them are retained (100% hollow particle ratio). Therefore, the hollow particle ratio can be determined from the weight change when the sample, dried overnight after filtration, is heat-treated to 800°C. In this case, a hollow particle ratio of 90% or more is preferable, and 95% or more is more preferable. In this case, a hollow particle ratio of 100% or less is preferable.

[0022] The BET specific surface area of ​​hollow silica particles is 1 to 100 m². ２ It is preferable that the amount is / g, and 1 to 50m ２ / g is more preferable. When the BET specific surface area is within the above range, not only is the above-described mechanism of action more likely to be expressed, but also the dispersibility of the hollow silica particles in the present composition is particularly likely to be improved, and it is easy to suppress an increase in the viscosity of the present composition. The BET specific surface area can be measured by a multipoint method using nitrogen gas after drying the hollow silica particles at 230 ° C until the pressure reaches 50 mTorr using a specific surface area measuring device (such as "TriStar II 3020" manufactured by Shimadzu Corporation).

[0023] Further, when the specific gravity (Ar density) of the hollow silica particles is A (g / cm ３ ), and the BET specific surface area is B (m ２ / g), the product of the two (A × B) is preferably 1 to 120 m ２ / cm ３ ). A × B is more preferably 80 m ２ / cm ３ or less, and even more preferably 40 m ２ / cm ３ or less. A × B is more preferably 2 m ２ / cm ３ or more, and even more preferably 2.5 m ２ / cm ３ or more. A × B can also be regarded as the specific surface area per volume when the hollow silica particles are dispersed in a solvent. For example, when the hollow silica particles are added to a resin, it represents the specific surface area of the portion occupied by the hollow silica particles in a predetermined volume in the resin. When A × B is within the above range, not only is the above-described mechanism of action more likely to be expressed, but also since the specific surface area of the hollow silica particles in the composition is small, it is easy to suppress an increase in the viscosity of the present composition. Further, when A × B is within the above range, it is easy to lower the relative permittivity and dielectric loss tangent of the cured product of the present composition and improve the electrical properties.

[0024] The sphericity of hollow silica particles is preferably between 0.75 and 1.0. When the sphericity is within this range, the hollow silica particles are less likely to break, it is easier to maintain the Ar density and specific surface area, and it is easier to lower the dielectric loss tangent. Sphericity is expressed as the average value obtained by measuring the maximum diameter (DL) and the minimum diameter (DS) perpendicular to it for any 100 particles in an image obtained by a scanning electron microscope (SEM), and calculating the ratio of the minimum diameter (DS) to the maximum diameter (DL) (DS / DL).

[0025] The average size of the primary particles of hollow silica particles (average primary particle diameter) is preferably in the range of 50 nm to 10 μm. More preferably, the average primary particle diameter is 70 nm or more, and even more preferably 100 nm or more. More preferably, the average primary particle diameter is 5 μm or less, and even more preferably 3 μm or less. When the average primary particle diameter of hollow silica particles is within the above range, they are easy to handle and it is easy to control the specific surface area, oil absorption, pore volume, and amount of SiOH on the particle surface. The average primary particle diameter of hollow silica particles is determined by measuring the size of any 100 primary particles from SEM observation images and taking the average of these values. The average primary particle diameter can also be considered to reflect the surface state of the secondary particles (aggregated particles) of the hollow silica particles and is a parameter that determines the specific surface area and oil absorption.

[0026] The hollow silica particles have the average primary particle diameter described above, preferably 35% or more of the total primary particles have a particle diameter within ±40% of the average primary particle diameter, more preferably 50% or more of the total primary particles have a particle diameter within ±40% of the average primary particle diameter, and even more preferably 70% or more of the total primary particles have a particle diameter within ±40% of the average primary particle diameter. In this case, the size of the hollow silica particles becomes more uniform, and shell defects of the hollow silica particles are less likely to occur.

[0027] The average particle diameter (D50) of the secondary particles (aggregated particles) of the hollow silica particles is 0.5 μm or more. Such D50 is more preferably 0.7 μm or more. Such D50 is preferably 10 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. When such D50 is within the above range, not only is the above-described mechanism of action more likely to be exhibited, but also the dispersion stability of the hollow silica particles in the present composition is likely to be improved, and the increase in the viscosity of the composition is likely to be suppressed. Further, it is easy to reduce the graininess in the cured product of the present composition.

[0028] Further, the coarse particle diameter (D90) of the secondary particles of the hollow silica particles is preferably 1 to 30 μm. Such D90 is more preferably 3 μm or more, and even more preferably 5 μm or more. Such D90 is more preferably 25 μm or less, and even more preferably 20 μm or less. When such D90 is within the above range, it is easy to increase the productivity of the hollow silica particles, and it is also easy to reduce the graininess in the cured product of the present composition. The particle diameter of the secondary particles of the hollow silica particles (the aggregation diameter at the time of aggregation of the primary particles) is determined by the laser diffraction / scattering method. That is, the particle size distribution is measured by the laser diffraction / scattering method, a cumulative curve is obtained with the total volume of the particle population as 100%, and the particle diameter at the point where the cumulative volume is 50% on the cumulative curve is D50, and the particle diameter at the point where the cumulative volume is 90% is D90.

[0029] The shell thickness of the hollow silica particles is preferably 0.01 to 0.3 when the diameter of the primary particle is 1, more preferably 0.02 or more, and even more preferably 0.03 or more. Further, the shell thickness of the hollow silica particles is more preferably 0.2 or less, and even more preferably 0.1 or less when the diameter of the primary particle is 1. When the shell thickness with respect to the diameter of the primary particle is within the above range, it is easy to maintain the strength of the hollow silica particles and easy to exhibit the characteristics based on the hollow shape. The shell thickness is determined by measuring the shell thickness of each particle by a transmission electron microscope (TEM).

[0030] In the hollow silica particles, SiO ２The content is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 99% by mass or more. SiO in hollow silica particles ２ The content may be 100% by mass, and is preferably 99.99% by mass or less. Here, SiO in hollow silica particles ２ The content refers to the amount of silica (SiO₂) contained in the shell layer that makes up the hollow silica particles. ２ This is the content of SiO in hollow silica particles, for example, "SiO in hollow silica particles" ２ "Having a content of 99% by mass or more" means that 99% by mass or more of the shell layer constituting the hollow silica particles is silica (SiO₂ ２ This means that it contains ). Residues in hollow silica particles include alkali metal oxides and silicates, alkaline earth metal oxides and silicates, carbon, etc. In other words, hollow silica particles may contain one or more metals M selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba. When metal M is included in hollow silica particles, it acts as a flux during firing, which reduces the specific surface area and tends to lower the dielectric loss tangent.

[0031] Metal M is incorporated into the hollow silica particles between the reaction step and the washing step during the manufacturing process. For example, metal M can be incorporated into the hollow silica particles by adding a metal salt of metal M to the reaction solution used to form the silica shell during the reaction step, or by washing the hollow silica precursor with a solution containing metal ions of metal M before firing. In the hollow silica particles of this composition, the concentration of metal M is preferably 50 ppm by mass or more and 1% by mass or less, more preferably 100 ppm by mass or more, even more preferably 150 ppm or more, and also preferably 1% by mass or less, more preferably 5000 ppm by mass or less, and even more preferably 1000 ppm by mass or less. When the total concentration of metal M is within the above range, the flux effect during firing promotes the condensation of bonded silanol groups, reducing the number of remaining silanol groups and thus lowering the dielectric loss tangent.

[0032] In the hollow silica particles in the present composition, the metal M is at least Na, and the Na content is preferably less than 1000 ppm by mass. In other words, in the present composition, the SiO ２ content in the hollow silica particles is 99% by mass or more, and the Na content is particularly preferably less than 1000 ppm by mass. In this case, not only is the above-described mechanism of action more likely to be exhibited, but the hollow silica particles are excellently balanced in their electrical properties and strength, and are also less likely to crack. The composition of the shell layer of the hollow silica particles can be measured by ICP emission spectrometry, flame atomic absorption spectrometry, or the like.

[0033] The hollow silica particles are preferably obtained by a production method including, for example, preparing a water-in-oil emulsion in which an oil phase is dispersed in water, which contains an aqueous phase, an oil phase, and a surfactant, and obtaining a hollow silica precursor in which a shell layer containing silica is formed on the outer periphery of the core in the water-in-oil emulsion, removing the core from the precursor, and performing heat treatment. Specifically, it is preferably produced by the method described in International Publication No. 2023 / 100676. When an alkali metal silicate is used as the silica raw material for forming the shell layer, the carbon (C) component derived from the raw material in the shell layer of the obtained hollow silica particles is less than when a silicon alkoxide is used as the silica raw material.

[0034] From the viewpoint of suppressing the adsorption of moisture and not deteriorating the electrical properties of the cured product of the present composition, the pore volume of the hollow silica particles is preferably 0.2 cm ３ / g or less. The pore volume is determined by the BJH method based on the nitrogen adsorption method using a specific surface area and pore distribution measuring device (for example, "BELSORP-miniIII" manufactured by Microtrac BEL Corporation, "Tristar II" manufactured by Micromeritics, etc.).

[0035] The surface of the hollow silica particles is treated with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group. The amount of such silane coupling agent applied is preferably in the range of 1 to 10 parts by mass per 100 parts by mass of hollow silica particles. When the surface of the hollow silica particles is treated with a silane coupling agent, the amount of remaining surface silanol groups is reduced, the surface becomes hydrophobic, which suppresses moisture adsorption and improves dielectric loss. Furthermore, the affinity with the epoxy resin in this composition is increased, making it easier to improve dispersibility, and thus improving the strength and low linear expansion of the cured product of this composition.

[0036] Examples of such silane coupling agents include silane coupling agents having an amino group, silane coupling agents having an epoxy group, and silane coupling agents having a (meth)acryloyloxy group. The amino group may be a primary amino group or a secondary amino group. Specific examples of silane coupling agents having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. Specific examples of silane coupling agents having an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyldimethoxysilane, and 3-glycidopropyltrimethoxysilane. Specific examples of silane coupling agents having a (meth)acryloyloxy group include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. Among these, silane coupling agents having an epoxy group or a methacrylloyloxy group are preferred. The treatment of the surface of hollow silica particles with a silane coupling agent can be confirmed by detecting peaks due to substituents of the silane coupling agent using IR. Furthermore, the amount of silane coupling agent attached can be measured by the amount of carbon.

[0037] The relative permittivity of hollow silica particles at 1 GHz is preferably 1.0 to 5.0, and more preferably 1.3 to 3.5. Furthermore, the dielectric loss tangent of hollow silica particles at 1 GHz is preferably 0.0001 to 0.05. The relative permittivity and dielectric loss tangent can be measured, for example, using a Keycom "Vector Network Analyzer E5063A" by the perturbation resonator method.

[0038] This composition may further contain solid silica particles. A configuration in which the composition includes both solid and hollow silica particles as silica particles is more preferable from the viewpoint of further improving the electrical properties of the cured product of this composition. The solid silica particles are preferably surface-treated with a silane coupling agent, more preferably with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group, and even more preferably with a silane coupling agent having an amino group, or an epoxy group or a methacrylicloyloxy group. In this case, it becomes easier to increase the content of hollow silica particles in this composition, and the above-described mechanism of action is more easily expressed in a balanced manner. The configurations of each silane coupling agent are the same as those used for surface treatment of hollow silica particles.

[0039] When the composition contains solid silica particles and hollow silica particles as silica particles, the ratio of hollow silica particles to the total amount of solid silica particles and hollow silica particles is preferably more than 1 volume%, more preferably 5 volume% or more, even more preferably 10 volume% or more, and particularly preferably 15 volume% or more. Such a ratio is preferably less than 50 volume%. When the ratio of hollow silica particles to the total amount of solid silica particles and hollow silica particles is within the above range, it is more preferable from the viewpoint of further improving the electrical properties of the cured product of the composition. The silica constituting the silica particles may be fused silica or crystalline silica. The average particle diameter (D50) of the solid silica particles is preferably 0.01 μm or more and 10 μm or less. The D50 of the solid silica particles is preferably 0.1 μm or more, and more preferably 0.2 μm or more. The average particle diameter (D50) of the solid silica particles is preferably 4 μm or less, and more preferably 3 μm or less. The average particle size of solid silica particles is determined by laser diffraction and scattering. Specifically, the particle size distribution is measured using laser diffraction and scattering, and a cumulative curve is calculated with the total volume of the particle collection set to 100%. The particle size at the point on this cumulative curve where the cumulative volume reaches 50% is defined as D50. The specific gravity of solid silica particles is 1.6 g / cm³. ３ 2.2g / cm or more ３ Preferably, it is 1.8 g / cm³. ３ 2.2g / cm or more ３ It is more preferable that it be less than . In this specification, solid silica particles refer to particles with a hollow ratio of less than 10%, and are distinguished from hollow silica particles by their hollow ratio.

[0040] The ratio of the average particle diameter (D50) of hollow silica particles to the average particle diameter (D50) of solid silica particles is preferably 0.1 to 10. Note that the D50 of hollow silica particles refers to the D50 of the secondary particles of the hollow silica particles as described above. If the D50 of solid silica particles is greater than the D50 of hollow silica particles, the ratio is more preferably 0.1 to 0.8. In this case, it is presumed that the solid silica particles have a buffering effect on the stress generated in the composition, and also promote the flow of the hollow silica particles, which are smaller than the solid silica particles, making them easier to homogenize. Therefore, the packing of silica particles when mounting the composition into electronic components and the like is easily improved, and the flowability into narrow gaps is also easily improved. If the D50 of solid silica particles is smaller than the D50 of hollow silica particles, the ratio is more preferably 2 to 10. In this case, it is presumed that the solid silica particles, which are in a loosely aggregated state, will buffer the stress acting on the composition and will also easily flow and homogenize among the hollow silica particles, which are larger than the solid silica particles. Therefore, the packing of silica particles when mounting this composition into electronic components and other devices is easily improved, and the fluidity into narrow gaps is also easily improved.

[0041] When this composition contains solid silica particles and hollow silica particles as silica particles, the silica particle content relative to the entire composition, in other words, the total content of solid silica particles and hollow silica particles relative to the entire composition, is preferably 40% by volume or more, and more preferably 50% by volume or more. The silica particle content is preferably 80% by volume or less. When the silica particle content is within the above range, the composition is easy to handle and the electrical properties of the cured product are more easily improved. The epoxy resin content relative to the entire composition is preferably 10% by mass or more, and more preferably 20% by mass or more. The epoxy resin content is preferably 40% by mass or less. The curing agent content having amino groups relative to the entire composition is preferably 5% by mass or more. The curing agent content having amino groups is preferably 15% by mass or less, and more preferably 10% by mass or less. Furthermore, in this composition, the ratio of the volume percentage of epoxy resin to the total volume percentage of solid silica particles and hollow silica particles is preferably 0.5 or more and 1 or less, and more preferably 0.6 or more and 0.9 or less. When the ratio is within this range, not only is the above-mentioned mechanism of action more easily expressed, but the silica particles and epoxy resin in this composition are more easily dispersed, and the properties based on the silica particles are more easily exhibited in the cured product of this composition (including molded products such as films).

[0042] This composition may further contain a curing accelerator as needed. Examples of curing accelerators include cycloamidine compounds such as 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene, and 5,6-dibutylamino-1,8-diazabicyclo[5.4.0]undecene-7; tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-methylimidazole. Examples of conventionally known compounds used in the curing of epoxy resins include imidazole compounds such as benzoyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2'-methylimidazolyl-(1'))-ethyl-s-triazine, and 2-heptadecylimidazole; and phenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. These may be used individually or in combination of two or more. If the composition contains a curing accelerator, its content is not particularly limited and can be appropriately selected as long as it is an amount that exhibits a curing-accelerating effect between the epoxy resin and the curing agent having an amino group. For example, it is preferably 0.1 to 40% by mass relative to the total amount of the epoxy resin and the curing agent having an amino group.

[0043] This composition may further contain a coupling agent. When a coupling agent is included, the interfacial adhesion between the epoxy resin constituting this composition and the silica particles, and the interfacial adhesion between this composition and the components of electronic parts tend to be stronger, and the filling properties tend to be improved. Examples of coupling agents include the silane coupling agents mentioned above; other silane coupling agents; silane compounds such as epoxysilane, mercaptosilane, alkylsilane, ureidosilane, and vinylsilane; titanium compounds; aluminum chelates; and aluminum / zirconium compounds. These may be used individually or in combination of two or more. When this composition contains a coupling agent, its content is preferably 0.05 to 10% by mass relative to the total mass of the epoxy resin and the curing agent having an amino group constituting this composition.

[0044] This composition may further contain a flexible agent as needed. When a flexible agent is included, the thermal shock resistance of this composition and the stress on semiconductor devices are easily reduced. Examples of flexible agents include rubber particles such as styrene-butadiene rubber, nitrile-butadiene rubber, butadiene rubber, urethane rubber, acrylic rubber, and silicone rubber. These may be used individually or in combination of two or more. The average primary particle diameter of such rubber particles is preferably 0.05 to 10 μm, and more preferably 0.1 to 5 μm. When the average primary particle diameter is within the above range, the dispersibility in this lipid composition and the stress reduction effect are easily improved, as are the penetration into fine gaps and fluidity of this composition, and the generation of voids and unfilled portions is easily suppressed. When this composition further contains a flexible agent, its content is preferably 1 to 30% by mass relative to the total components of this composition other than silica particles.

[0045] This composition may further contain an ion trapping agent as needed. When an ion trapping agent is included, the migration resistance, moisture resistance, and high-temperature storage characteristics of semiconductor devices such as ICs to which this composition is applied tend to improve.

[0046] This composition may further contain other additives, such as colorants, leveling agents, surfactants, inorganic fillers different from the silica particles described above, thixotropic agents, viscosity modifiers, defoaming agents, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, conductive agents, mold release agents, and flame retardants, to the extent that they do not impair the effects of the present invention.

[0047] This composition is obtained by mixing hollow silica particles surface-treated with the silane coupling agent described above, an epoxy resin, a curing agent having amino groups, and, if necessary, solid silica particles, additives, etc. This composition may be obtained by mixing the hollow silica particles, epoxy resin, and curing agent having amino groups all at once, or by mixing them in multiple stages. When mixing, it is preferable to mix in such a way that the total mass of the hollow silica particles, epoxy resin, curing agent having amino groups, and, if necessary, solid silica particles, additives, etc. does not change substantially, and mixing in a closed system is preferable. As a result, a composition is obtained in which each component is uniformly mixed and highly degassed.

[0048] The mixing apparatus for obtaining this composition is not particularly limited as long as it can sufficiently disperse and mix each component. Examples include stirring devices equipped with blades such as Henschel mixers, pressure kneaders, Banbury mixers, and planetary mixers; grinding devices equipped with media such as ball mills, attritors, basket mills, sand mills, sand grinders, Dino mills, disper mats, SC mills, spike mills, and agitator mills; and dispersion devices equipped with other mechanisms such as microfluidizers, nanomizers, ultimateizers, ultrasonic homogenizers, desolvers, dispersers, high-speed impellers, thin-film swirling high-speed mixers, rotational and revolving agitators, and V-type mixers. The mixing method may be either batch or continuous.

[0049] The composition is preferably liquid at room temperature (25°C). The viscosity of the liquid composition is preferably 200 Pa·s or less, and more preferably 100 Pa·s or less. The viscosity of the composition is preferably 0.01 Pa·s or more, and more preferably 0.1 Pa·s or more. In this case, not only is the above-described mechanism of action more easily expressed, but the composition produces less foam, and it is easier to ensure fluidity and permeability that can accommodate the miniaturization of electronic components, the fine pitch of connection terminals of semiconductor elements, and the fine wiring of wiring boards in recent years. In addition, the cured product of the composition becomes denser, and physical properties based on silica particles are more easily expressed. The viscosity of the composition is determined by measuring the composition using a B-type viscometer with an appropriate rotor under conditions of 25°C and a rotation speed of 5 rpm.

[0050] This composition can be used for electronic component devices such as encapsulants, build-up films, and underfill materials for semiconductor devices, and is preferably used as an encapsulant or underfill material for semiconductor devices. For example, a specific example of using this composition as an underfill material is to apply this composition to one end of a semiconductor element while maintaining a substrate equipped with a semiconductor element at 70 to 130°C, fill the gap between the substrate and the semiconductor element with the composition by capillary action, and then seal the gap between the substrate and the semiconductor element by curing the composition while maintaining the substrate at 80 to 200°C. The filling time is preferably within 1200 seconds. The curing time of this composition is preferably 0.1 to 6 hours.

[0051] This composition can be suitably used as a encapsulant, build-up film, or underfill material for semiconductor devices in which electronic components such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors, resistor arrays, coils, and switches are mounted on support members such as lead frames, pre-wired tape carriers, rigid and flexible wiring boards, glass, and silicone wafers. In particular, it is suitable as an underfill material for flip-chip devices, and specifically, it can be suitably used as an underfill material for semiconductor devices such as flip-chip BGA / LGA and COF (Chip On Film), in which semiconductor elements are flip-chip bonded by bump connection to wiring formed on rigid and flexible wiring boards or glass. In other words, the present invention also includes encapsulants, build-up films, or underfill materials for semiconductor devices made from this composition.

[0052] The present invention also relates to a cured product of the composition. The cured product of the composition may be a cured product used as a encapsulant or underfill material for the semiconductor device described above, or it may be in the form of a molded product such as the build-up film described above.

[0053] The relative permittivity (Dk) of the cured product of this composition is preferably 3.5 or less, more preferably 3.1 or less, at a frequency of 10 GHz. The relative permittivity is preferably 1.5 or more. Furthermore, the dielectric loss tangent (Df) of the cured product of this composition is preferably 0.022 or less, more preferably 0.020 or less, even more preferably 0.012 or less, and particularly preferably 0.009 or less, at a frequency of 10 GHz. When the relative permittivity and dielectric loss tangent of the cured product at a frequency of 10 GHz are within the above ranges, the electrical properties are excellent, and transmission loss in the circuit is easily suppressed. The relative permittivity and dielectric loss tangent can be measured, for example, using the apparatus described in the examples.

[0054] The average linear expansion coefficient of the cured product of this composition is preferably 10 to 80 ppm / °C. When the average linear expansion coefficient is within the above range, the electrical properties tend to be excellent. The average linear expansion coefficient is determined using a thermomechanical analyzer (for example, "TMA7100" manufactured by Hitachi High-Tech Science Corporation), by heating the cured product under a load of 98 mN and a heating rate of 5°C / min, measuring the temperature increase from 25°C to 230°C using the compression method, and obtaining the linear expansion coefficient from the tangent slope from 80°C to 100°C.

[0055] Although the present composition and its cured product have been described above, the present invention is not limited to the configuration of the embodiments described above. For example, the present composition and its cured product (including molded products such as films) may have other arbitrary configurations added to the configuration of the above embodiments, or may be replaced with any arbitrary configuration that performs similar functions.

[0056] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. 1. Preparation of each component [Silica particles] <Solid silica particles> Solid silica particle 1: "SO-C2" manufactured by Admatex, Inc., median diameter 0.5 μm Solid silica particle 2: Solid silica particle 1 surface-treated with "KBM-403" (silane coupling agent having epoxy groups) manufactured by Shin-Etsu Chemical Co., Ltd. <Hollow silica particles> Hollow silica particles 1: Hollow silica particles made from AGC's "HS-200" (median diameter 2.0 μm) surface-treated with Shin-Etsu Chemical's "KBM-403" (silane coupling agent with epoxy groups) Hollow silica particles 2: Hollow silica particles made from AGC's "HS-200" surface-treated with Shin-Etsu Chemical's "KBM-503" (silane coupling agent with methacryloyloxy groups) Hollow silica particles 3: Hollow silica particles made from AGC's "HS-200" surface-treated with Shin-Etsu Chemical's "KBM-573" (silane coupling agent with amino groups) Hollow silica particles 4: Hollow silica particles made from AGC's "HS-200" surface-treated with Shin-Etsu Chemical's "KBM-803" (silane coupling agent with mercapto groups) Hollow silica particles Hollow silica particle 5: Hollow silica particles manufactured by AGC Corporation, "HS-070" (median diameter 0.5 μm), surface-treated with Shin-Etsu Chemical Co., Ltd.'s "KBM-403" (silane coupling agent with epoxy groups) Hollow silica particle 6: Hollow silica particles manufactured by AGC Corporation, "HS-070" (median diameter 0.5 μm), surface-treated with Shin-Etsu Chemical Co., Ltd.'s "KBM-573" (silane coupling agent with amino groups) Hollow silica particle 7: Hollow silica particles manufactured by JGC Catalysts & Chemicals Co., Ltd., "Thru-Ria (registered trademark) 4100", median diameter 0.06 μm, surface-treated with a silane coupling agent with epoxy groups Hollow silica particle 8: Hollow silica particles with a median diameter of 0.5 μm, not surface-treated with a silane coupling agent (manufactured by JGC Catalysts & Chemicals Co., Ltd.) The median diameter of the silica particles was measured using a diffraction scattering particle distribution analyzer (MT3300) manufactured by Microtrac-Bell. The median value of the particle distribution (diameter) was measured and represents the average particle diameter (D50) of the silica particles. The measurement was performed twice, and the average value was calculated.

[0057] [Epoxy Resins] Epoxy Resin 1: "jER806" manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, epoxy group equivalent 167 g / eq Epoxy Resin 2: "jER630" manufactured by Mitsubishi Chemical Corporation, glycidylamine type epoxy resin, epoxy group equivalent 96 g / eq Epoxy Resin 3: "HP-4032D" manufactured by DIC Corporation, naphthalene type epoxy resin, epoxy group equivalent 141 g / eq [Curing Agents] Amine-based curing agent 1: "jER Cure WA" manufactured by Mitsubishi Chemical Corporation, diaminobenzenes, active hydrogen equivalent 45 g / mol Amine-based curing agent 2: "Kaya Hard A-A" manufactured by Nippon Kayaku Co., Ltd., bisaniline, active hydrogen equivalent 64 g / mol [Other Components] Coloring agent: "MA-100" manufactured by Mitsubishi Chemical Corporation (carbon black) Coupling agent: "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd. (silane coupling agent with epoxy groups)

[0058] 2. Examples of Manufacturing Curable Compositions [Example 1] A curable composition 1 was obtained by mixing parts by mass of silica particles such that the composition contained 45% by volume of solid silica particles 1 and 5% by volume of hollow silica particles 1, parts by mass of epoxy resins such that epoxy resin 1, epoxy resin 2, and epoxy resin 3 were included in the total epoxy resin content ratios of epoxy resin 1 (50% by mass), epoxy resin 2 (25% by mass), and epoxy resin 3 (25% by mass), and parts by mass of amine-based curing agents such that amine-based curing agent 1 and amine-based curing agent 2 were included in the total curing agent content ratios of amine-based curing agent 1 (70% by mass) and amine-based curing agent 2 (30% by mass). When mixing, a coloring agent and a coupling agent were also used, with the coloring agent at 0.5 phr and the coupling agent at 3.0 phr relative to the total mass of epoxy resin and curing agent. The total content of silica particles, epoxy resin, and curing agent in curable composition 1 was 67% by mass, 24% by mass, and 9% by mass, respectively.

[0059] [Examples 2 to 14] Curable compositions 2 to 14 were obtained by performing the same procedure as in Example 1, except that the volume % content of solid silica particles, the type and volume % content of hollow silica particles were changed as shown in Table 1.

[0060] 3. Evaluation of Curable Compositions 3-1. Relative Permittivity (Dk) The curable compositions obtained in each example were poured into a mold and molded under conditions of a mold temperature of 150°C and a curing time of 2 hours to obtain a plate-shaped cured product (80 mm long, 40 mm wide, 0.2 mm thick). The obtained cured product was used as a test piece, and the relative permittivity (Dk) at 25±3°C and 10 GHz was measured using a dielectric constant measuring device "Network Analyzer N5227A" (manufactured by Agilent Technologies, Inc.) and evaluated according to the following criteria. <Evaluation Criteria for Dk> ◎: Dk is 3.1 or less ○: Dk is greater than 3.1 and 3.3 or less △: Dk is greater than 3.3 and 3.4 or less ×: Dk is greater than 3.4

[0061] 3-2. Pot Life For each curable composition obtained in the pot life example, the viscosity immediately after preparation (Pa·s; initial viscosity) and the viscosity every four hours while kept in a sealed container at 25°C were measured using a Toki Sangyo Co., Ltd. Type B viscometer "TVB-10" (rotor used: rotor H7), rotated at 25°C and 5 rpm for 1 minute. The time until the viscosity increased to more than twice the initial viscosity was determined, and the pot life was evaluated according to the following criteria. <Evaluation Criteria> ◎: More than 24 hours until viscosity increased to more than twice the initial viscosity ○: More than twice the initial viscosity in 16 hours or more but less than 24 hours △: More than twice the initial viscosity in 8 hours or more but less than 16 hours ×: More than twice the initial viscosity in less than 8 hours

[0062] 3-3. Viscosity (110°C) The viscosity (Pa·s; initial viscosity) of the curable compositions obtained in each example immediately after preparation was measured using a Toki Sangyo Co., Ltd. Type B viscometer "TVB-10" (rotor used: rotor H7) by rotating at 110°C and 5 rpm for 1 minute, and evaluated according to the following criteria. <Evaluation Criteria> ◎: Initial viscosity is 15.0 Pa·s or less ○: Initial viscosity is greater than 15.0 Pa·s and 18.0 Pa·s or less △: Initial viscosity is greater than 18.0 Pa·s and 20.0 Pa·s or less ×: Initial viscosity is greater than 20.0 Pa·s

[0063] 3-4. Average linear expansion coefficient (CTEα1) The curable compositions obtained in each example were poured into a mold and molded under conditions of a mold temperature of 150°C and a curing time of 2 hours to form a prismatic cured product (3 mm long, 3 mm wide, 15 mm high). Using a Hitachi High-Tech Science Corporation thermomechanical analyzer "TMA7100", the product was heated with a load of 98 mN and a heating rate of 5°C / min, and the temperature was measured from 25°C to 230°C using the compression method. The average linear expansion coefficient was determined from the tangent slope from 80°C to 100°C and evaluated according to the following criteria. <Evaluation Criteria> ◎: CTEα1 value is 35 or less ○: CTEα1 value is greater than 35 and 40 or less △: CTEα1 value is greater than 40 and 45 or less ×: CTEα1 value is greater than 45

[0064] The results are shown in Table 1. The cured products formed from the curable compositions of Examples 1-4 and 6-10 exhibit a good balance of relative permittivity, pot life, viscosity, and average linear expansion coefficient.

[0065] The curable composition of the present invention exhibits excellent handling properties (pot life) and penetration into narrow gaps, as well as excellent electrical properties (low dielectric constant, low dielectric loss tangent, etc.) and moisture resistance. It can form cured products that also possess mechanical properties, insulation, low linear expansion, and adhesiveness. Taking advantage of these properties, the curable composition of the present invention can be effectively used in electronic component devices such as encapsulants, build-up films, or underfill materials for semiconductor devices.

Claims

1. A curable composition comprising an epoxy resin, a curing agent having an amino group, and hollow silica particles surface-treated with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group, wherein the average particle diameter (D50) of the hollow silica particles is 0.5 μm or more.

2. The curable composition according to claim 1, wherein the curing agent is an aromatic amine compound.

3. The curable composition according to claim 1, wherein the active hydrogen equivalent of the curing agent is 40 to 80 g / mol.

4. The curable composition according to claim 1, wherein the silane coupling agent is a silane coupling agent having an amino group.

5. The curable composition according to claim 1, wherein the silane coupling agent is a silane coupling agent having an epoxy group or a methacrylicloyloxy group.

6. The curable composition according to claim 1, further comprising solid silica particles.

7. The curable composition according to claim 6, wherein the solid silica particles are hollow silica particles surface-treated with a silane coupling agent having an amino group or a group capable of addition reaction with an amino group.

8. The curable composition according to claim 7, wherein the silane coupling agent is a silane coupling agent having an amino group, or a silane coupling agent having an epoxy group or a methacrylicloyloxy group.

9. The curable composition according to claim 8, wherein the average particle size of the solid silica particles is 0.01 to 10 μm.

10. The curable composition according to claim 8, wherein the ratio of the average particle diameter (D50) of the hollow silica particles to the average particle diameter (D50) of the solid silica particles is 0.1 to 10.

11. The curable composition according to claim 8, wherein the ratio of the hollow silica particles to the total amount of the solid silica particles and the hollow silica particles is 5% by volume or more.

12. The curable composition according to claim 8, wherein the total content of solid silica particles and hollow silica particles relative to the entire curable composition is 50% by volume or more.

13. A cured product of a curable composition according to any one of claims 1 to 12.

14. A curable composition according to any one of claims 1 to 12, for use in electronic component devices.

15. A curable composition according to any one of claims 1 to 12, which is for use as a encapsulant, build-up film, or underfill material for semiconductor devices.

Images