KR20200094792A - Epoxy resin composition for sealing a ball grid array package, cured epoxy resin, and electronic component device - Google Patents

Abstract

The epoxy resin composition for sealing a BGA package includes an epoxy resin containing a bisphenol F-type epoxy resin, a curing agent, alumina particles, and no silica particles, or alumina particles, and further comprising silica particles, alumina particles and silica An inorganic filler containing more than 0% by mass and 15% by mass or less with respect to the total amount of particles, a plasticizer, and the content of the inorganic filler is 75% by volume to 84% by volume.

Description

Epoxy resin composition for sealing a ball grid array package, cured epoxy resin, and electronic component device

The present disclosure relates to an epoxy resin composition for sealing a ball grid array package, an epoxy resin cured product, and an electronic component device.

The demand for high-density mounting due to the miniaturization and thinning of electronic devices has increased rapidly in recent years. For this reason, in the semiconductor package, instead of the conventional pin insertion type, a surface mounting type suitable for high density mounting is mainly used. The surface-mounted semiconductor package is mounted by directly soldering a printed circuit board or the like. As a general mounting method, a method of heating and mounting the entire semiconductor package by an infrared reflow method, a gas phase reflow method, a solder dip method, or the like can be mentioned.

In recent years, in order to increase the mounting density, area mounting packages such as ball grid arrays (hereinafter also referred to as BGAs) are widely used among surface-mounted semiconductor packages. The BGA package is a single-sided resin sealed package in which the semiconductor element mounting surface of the substrate is sealed with a resin composition. As a resin composition for sealing, an epoxy resin composition is widely used from the viewpoint of balance of various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with an insert.

On the other hand, in the field of electronic components in recent years, high-speed and high-density are advancing, and accompanying it, the calorific value of the electronic components has significantly increased. In addition, there is an increasing demand for electronic components operating under high temperatures. For this reason, improvement in thermal conductivity is required for plastics used in electronic components, especially cured products of epoxy resins. In particular, in the BGA package, high heat conductivity of the resin composition for sealing is required from the demand for downsizing and high density. In a BGA package or the like, as a method of improving the thermal conductivity of a cured product of an epoxy resin, a method of using a high thermal conductivity inorganic filler such as alumina, a resin having a low viscosity and a small amount of fine silica are used in combination to increase the filling amount of the inorganic filler The method of making it, etc. has been reported (for example, refer patent document 1).

Japanese Patent No. 4188634

However, if the amount of alumina filling in the epoxy resin composition is increased for the purpose of high heat conduction, fluidity may deteriorate and the moldability may be impaired. In Patent Document 1, a small amount of fine silica is mixed with an alumina filler, and a specific biphenyl-type epoxy resin having a relatively low viscosity is used to promote filler filling. However, in the method of patent document 1, there existed a problem in the balance of thermal conductivity and fluidity.

Accordingly, the present disclosure is excellent in fluidity, an epoxy resin composition for sealing a BGA package excellent in thermal conductivity when cured, an epoxy resin cured product obtained by curing the epoxy resin composition, and sealed by the epoxy resin cured product An object of the present invention is to provide an electronic component device having an element.

The following embodiments are included in the solution means of the said subject.

<1> An epoxy resin containing a bisphenol F-type epoxy resin, a curing agent, alumina particles and no silica particles, or alumina particles, and further comprising silica particles with respect to the total amount of alumina particles and silica particles 0 An epoxy resin composition for sealing a ball grid array package, comprising an inorganic filler containing more than 15% by mass, and a plasticizer, wherein the content of the inorganic filler is 75% to 84% by volume.

<2> The epoxy resin composition for sealing the ball grid array package according to <1>, wherein the epoxy resin further comprises a biphenyl-type epoxy resin.

<3> The inorganic filler contains alumina particles and does not contain silica particles, or contains alumina particles and further contains silica particles in an amount of more than 0% by mass and 10% by mass or less with respect to the total amount of alumina particles and silica particles. The epoxy resin composition for sealing a ball grid array package as described in <1> or <2>.

<4> The epoxy resin composition for sealing a ball grid array package according to any one of <1> to <3>, wherein the curing agent contains a phenol curing agent having a hydroxyl group equivalent of 150 g/eq or less.

<5> The epoxy resin composition for sealing a ball grid array package according to any one of <1> to <4>, wherein the curing agent contains a phenol resin having three or more phenolic hydroxyl groups in one molecule.

<6> The epoxy resin composition for sealing a ball grid array package according to any one of <1> to <5>, wherein the curing agent contains a triphenylmethane type phenol resin.

<7> The epoxy resin composition for sealing a ball grid array package according to any one of <1> to <6>, wherein the porosity of the inorganic filler is 18 vol% or less.

<8> In the particle size distribution based on the volume of the inorganic filler, the proportion of particles having a particle diameter of 1 µm or less is 9% by volume or more, and the proportion of particles having a particle diameter of 1 µm or more and 10 µm or less is 45% by volume or less. , The proportion of particles having a particle diameter of more than 10 μm and 30 μm or less is 20% by volume or more, and the proportion of particles having a particle diameter of more than 30 μm is 18% by volume or more, according to any one of <1> to <7>. Epoxy resin composition for sealing a ball grid array package.

<9> In the particle size distribution based on the volume of the inorganic filler, the proportion of particles having a particle diameter of 1 µm or less is 11% by volume or more, and the proportion of particles having a particle diameter of 1 µm or more and 10 µm or less is 40% by volume or less. The epoxy resin for sealing a ball grid array package according to <8>, wherein the proportion of particles having a particle diameter of more than 10 µm and 30 µm or less is 22% by volume or more, and the proportion of particles having a particle diameter of 30 µm or more is 20% by volume or more. Composition.

<10> An epoxy resin cured product obtained by curing the epoxy resin composition for sealing the ball grid array package according to any one of <1> to <9>.

An electronic component device having a <11> element and the cured epoxy resin according to <10> sealing the element and having the form of a ball grid array package.

According to the present disclosure, an epoxy resin composition for sealing a BGA package having excellent fluidity and excellent thermal conductivity when cured, an epoxy resin cured product obtained by curing the epoxy resin composition, and a device sealed by the epoxy resin cured product There is provided an electronic component device having a.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, its components (including element steps, etc.) are not essential except where specifically indicated. The same applies to numerical values and ranges, and the present invention is not limited.

In the present disclosure, the word "process" includes, in addition to a process independent from other processes, when the purpose of the process is achieved even when it is not clearly distinguishable from other processes, the process is also included.

In the numerical range indicated by using "to" in this disclosure, the numerical values described before and after "to" are included as the minimum value and the maximum value, respectively.

In the numerical ranges described in stages during the present disclosure, the upper or lower limit values described in one numerical range may be substituted with the upper or lower limit values of the numerical ranges in another stepwise description. In addition, in the numerical range described during this disclosure, the upper limit value or the lower limit value of the numerical range may be substituted with the values shown in the examples.

In the present disclosure, each component may contain a plurality of substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component means the content or content of the sum of the substances of the plurality of substances present in the composition, unless otherwise specified.

In this disclosure, the particle|grains corresponding to each component may contain multiple types. When a plurality of particles corresponding to each component are present in the composition, the particle diameter of each component means a value for a mixture of the plurality of particles present in the composition, unless otherwise specified.

<Epoxy resin composition for sealing BGA package>

The epoxy resin composition for sealing a BGA package of the present disclosure (hereinafter, also simply referred to as an epoxy resin composition) includes an epoxy resin containing a bisphenol F-type epoxy resin, a curing agent, alumina particles, and no silica particles, or alumina. An inorganic filler containing a particle and a plasticizer further comprising 0 to 15% by mass or less based on the total amount of alumina particles and silica particles containing silica particles, and the content of the inorganic filler is 75% to 84% by volume to be.

The epoxy resin composition of the present disclosure is excellent in fluidity and excellent in thermal conductivity when cured. Although the reason is not clear, it can be considered as follows. Generally, when the filling rate of alumina particles is increased in the epoxy resin composition, high thermal conductivity is obtained. However, with high charge conversion of alumina particles, the fluidity of the composition decreases, which causes wire flow and the like. On the other hand, it is considered that the epoxy resin composition of the present disclosure contains bisphenol F-type epoxy resin and a plasticizer, so that even when alumina particles are contained at a high ratio when used as a composition, fluidity is easily guaranteed. In addition, it is considered that this makes it possible to make the inorganic filler more highly charged and further improve the thermal conductivity when cured.

The epoxy resin composition of the present disclosure is used for sealing BGA packages. The BGA package refers to a semiconductor package in which a plurality of metal bumps are arranged in a lattice on a substrate of the package. The BGA package is manufactured by mounting an element on the surface of a substrate on which a metal bump is formed on the back surface, connecting the element and wiring formed on the substrate by bump or wire bonding, and sealing the element. CSP (Chip Size Package), etc., in which the outer diameter dimension is reduced to the same level as that of the device, is also one form of the BGA package.

[Epoxy resin]

The epoxy resin composition of the present disclosure contains an epoxy resin containing a bisphenol F-type epoxy resin. The epoxy resin composition may contain an epoxy resin other than the bisphenol F-type epoxy resin.

(Bisphenol F-type epoxy resin)

In the present disclosure, the bisphenol F-type epoxy resin refers to diglycidyl ether of substituted or unsubstituted bisphenol F. Bisphenol F-type epoxy resins may be used alone or in combination of two or more.

As a bisphenol F-type epoxy resin, the epoxy resin represented with the following general formula (I) is mentioned, for example.

In General Formula (I), R1 to R8 represent a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. n is an average value and represents the number of 0-10.

The bisphenol F type epoxy resin represented by the said general formula (I) can be obtained by making epichlorohydrin react with a bisphenol F compound by a well-known method.

In general formula (I), as R1 to R8, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t-butyl group, such as an alkyl group having 1 to 18 carbon atoms, a vinyl group, and allyl An alkenyl group having 1 to 18 carbon atoms such as a group and a butenyl group, an aryl group, and the like, and is preferably a hydrogen atom or a methyl group.

In the general formula (I), n is an average value, represents a number from 0 to 10, and is preferably a number from 0 to 4. If n is 10 or less, the melt viscosity of the resin component is not too high, and the viscosity at the time of melt molding of the epoxy resin composition decreases, thereby suppressing occurrence of poor filling, deformation of the bonding wire (gold wire connecting the element and the lead), and the like. Tend to be.

Examples of the bisphenol F-type epoxy resin include 4,4'-methylene bis (2,6-dimethylphenol) diglycidyl ether as the main component, and 4,4'-methylene bis (2,3, 6-trimethylphenol) epoxy resins having diglycidyl ether as a main component, and epoxy resins having 4,4'-methylenebisphenol diglycidyl ether as a main component. Especially, the epoxy resin which has the main component of diglycidyl ether of 4,4'-methylenebis (2,6-dimethylphenol) is preferable. As a bisphenol F-type epoxy resin, YSLV-80XY (Shinnitetsu Sumkin Chemical Co., Ltd., a brand name) etc. can be obtained as a commercial item.

The content ratio of the bisphenol F-type epoxy resin is not particularly limited, preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. The content ratio of the bisphenol F-type epoxy resin may be 100% by mass or less, 75% by mass or less, or 50% by mass or less.

The epoxy equivalent of the bisphenol F-type epoxy resin is not particularly limited. From the viewpoint of various property balances such as moldability, downflow properties, and electrical reliability, the epoxy equivalent of the bisphenol F-type epoxy resin is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq desirable. The epoxy equivalent of the epoxy resin is a value measured by a method according to JIS K 7236:2009. It is the same below.

When the bisphenol F-type epoxy resin is solid, its softening point or melting point is not particularly limited. The softening point or melting point of the bisphenol F-type epoxy resin is preferably 40°C to 180°C from the viewpoint of moldability and reflowability, and more preferably 50°C to 130°C from the viewpoint of handling properties when preparing the epoxy resin composition. The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method according to JIS K 7234:1986 (return method). It is the same below.

(Biphenyl type epoxy resin)

The epoxy resin composition may contain a biphenyl-type epoxy resin in addition to the bisphenol F-type epoxy resin. The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, the epoxy resin represented by the following general formula (II) etc. are mentioned.

In General Formula (II), R1 to R8 represent a hydrogen atom or a substituted or unsubstituted monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. n is an average value and represents the number of 0-10.

The biphenyl-type epoxy resin represented by the general formula (II) can be obtained by reacting a biphenol compound with epichlorohydrin by a known method.

In general formula (II), as R1 to R8, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, an alkyl group having 1 to 18 carbon atoms such as a t-butyl group, vinyl group, allyl An alkenyl group having 1 to 18 carbon atoms such as a group and a butenyl group, an aryl group, and the like, and is preferably a hydrogen atom or a methyl group.

In the general formula (II), n is an average value, represents a number from 0 to 10, and is preferably a number from 0 to 4.

Examples of the biphenyl-type epoxy resin include 4,4'-bis(2,3-epoxypropoxy) biphenyl or 4,4'-bis(2,3-epoxypropoxy)-3,3',5 Epoxy resin based on ,5'-tetramethylbiphenyl, epichlorohydrin and 4,4'-biphenol or 4,4'-(3,3',5,5'-tetramethyl)biphenol And epoxy resins obtained by reacting. Among them, an epoxy resin containing 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl as a main component is preferable. As a biphenyl type epoxy resin, YX-4000 (Mitsubishi Chemical Co., Ltd., brand name), YL-6121H (Mitsubishi Chemical Co., Ltd., brand name) etc. are available as a commercial item.

When the epoxy resin contains a biphenyl-type epoxy resin, the content ratio of the biphenyl-type epoxy resin is not particularly limited, preferably 20 mass% or more, more preferably 30 mass% or more, and more preferably 50 mass% of the total amount of the epoxy resin. % Or more is more preferable. The content ratio of the biphenyl-type epoxy resin may be less than 100% by mass, 90% by mass or less, 80% by mass or less, or 10% by mass or less.

The epoxy equivalent of the biphenyl-type epoxy resin is not particularly limited. From the viewpoint of various property balances such as moldability, downflow properties, and electrical reliability, the epoxy equivalent of the biphenyl-type epoxy resin is preferably 100 g/eq to 1000 g/eq, and more preferably 150 g/eq to 500 g/eq. Do.

When the biphenyl-type epoxy resin is solid, its softening point or melting point is not particularly limited. The softening point or melting point of the epoxy resin is preferably 40°C to 180°C from the viewpoint of moldability and reflowability, and more preferably 50°C to 130°C from the viewpoint of handling properties when preparing the epoxy resin composition.

(Other epoxy resins)

The epoxy resin composition may contain epoxy resins other than bisphenol F-type epoxy resins and biphenyl-type epoxy resins (also referred to as "other epoxy resins"). The "other epoxy resin" is not particularly limited, and is preferably an epoxy resin having two or more epoxy groups in one molecule. As an epoxy resin having two or more epoxy groups in one molecule, stilbene type epoxy resin, sulfur atom-containing epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, salicylaldehyde type epoxy resin, copolymerization of naphthol and phenols Type epoxy resins, aralkyl type epoxy resins, diphenylmethane type epoxy resins (except bisphenol F type epoxy resins) and triphenylmethane type epoxy resins. "Other epoxy resins" may be used alone or in combination of two or more.

The content ratio of "other epoxy resins" is not particularly limited, and is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and further preferably 5% by mass or less, based on the total amount of the epoxy resin. Especially preferred.

The epoxy equivalent of "other epoxy resin" is not particularly limited. From the viewpoints of various property balances such as formability, downflow properties, and electrical reliability, the epoxy equivalent of "other epoxy resins" is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq. Do.

When the "other epoxy resin" is a solid, its softening point or melting point is not particularly limited. From the viewpoint of formability and reflowability, the softening point or melting point of the "other epoxy resin" is preferably 40°C to 180°C, and more preferably 50°C to 130°C from the viewpoint of handling properties when preparing the epoxy resin composition.

The total content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass from the viewpoints of strength, fluidity, heat resistance, and moldability.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule, and may include an epoxy resin (also referred to as a polyfunctional epoxy resin) having three or more epoxy groups in one molecule. As will be described later, when the epoxy resin composition contains an organophosphorus compound as a curing accelerator, the content of the polyfunctional epoxy resin to the total mass of the epoxy resin is 10% by mass or less from the viewpoint of controlling the warpage of the package during mounting. It is preferable, it is more preferable that it is 5 mass% or less, it is more preferable that it is 1 mass% or less, and it is especially preferable that it is substantially 0 mass %. The content rate of "substantially 0% by mass" refers to a content rate such that the effect of the polyfunctional epoxy resin on the warpage of the package during mounting is not observed.

[Curing agent]

The epoxy resin composition of the present disclosure contains a curing agent. The curing agent is not particularly limited as long as it can react with the epoxy resin. From the viewpoint of improving heat resistance, the curing agent is preferably a compound having two or more phenolic hydroxyl groups in one molecule (hereinafter also referred to as a phenol curing agent). The phenol curing agent may be a low molecular weight phenolic compound or a phenolic resin obtained by polymerizing a low molecular weight phenolic compound. From the viewpoint of thermal conductivity, it is preferable that the phenol curing agent is a phenol resin. The curing agent may be used alone or in combination of two or more.

The phenol curing agent preferably contains a phenol resin having two or more phenolic hydroxyl groups in one molecule, and more preferably contains a phenol resin (also referred to as a polyfunctional phenol resin) having three or more phenolic hydroxyl groups in one molecule. desirable.

The phenol resin is not particularly limited, and biphenylene type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, benzaldehyde type phenol resin and aralkyl type phenol resin copolymer resin, paraxylene modified phenol resin, triphenyl And methane type phenol resins. Especially, a triphenylmethane type phenol resin is preferable from a moldability viewpoint. From the viewpoint of fluidity, paraxylene-modified phenol resins are preferred.

The paraxylene-modified phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a paraxylene skeleton as a raw material. For example, it is preferable that it is a phenol resin represented by the following general formula (XV).

Among the phenol resins represented by the following general formula (XV), XL-225 (Mitsui Chemical Co., Ltd.), XLC (Mitsui Chemical Co., Ltd.), MEH-7800 (Meiwa Kasei Chemical Co., Ltd., Brand name) and the like are available as commercial products.

In formula (XV), R ³⁰ represents a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i each independently represents the integer of 0-3. n is an average value and is a number of 0-10. Incidentally, in the formula (XV), hydrogen atoms present on the aromatic ring are not indicated.

The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a triphenylmethane skeleton as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferred.

Among the phenol resins represented by the following general formula (XVI), i is 0 and k is 0. MEH-7500 (Meiwa Kasei Co., Ltd., trade name) is available as a commercial product.

In Formula (XVI), R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 18 carbon atoms, and each may be the same or different. i is an integer of 0-3 each independently, and k is an integer of 0-4 each independently. n is an average value and is a number of 0-10. Incidentally, in the formula (XVI), hydrogen atoms present on the aromatic ring are not indicated.

The hydroxyl group equivalent of the curing agent is not particularly limited, it is preferably 500 g/eq or less, more preferably 400 g/eq or less, and even more preferably 300 g/eq or less. The lower limit of the hydroxyl group equivalent of the curing agent is preferably 50 g/eq or more, more preferably 60 g/eq or more, and even more preferably 70 g/eq or more. The range of hydroxyl group equivalents of the curing agent is preferably 50 g/eq to 500 g/eq, more preferably 50 g/eq to 400 g/eq, and even more preferably 50 g/eq to 300 g/eq.

Especially, it is preferable that a hardening|curing agent contains the hydroxyl group equivalent 150g/eq or less of a phenol hardening agent (it is also hereafter referred to as a "specific phenol hardening agent"). When the curing agent contains a specific phenolic curing agent, even when the inorganic filler containing alumina particles is included, there is a tendency that a decrease in moldability is suppressed. This is considered to be one factor that the crosslinking density at the time of curing increases and the curability improves. In addition, when the curing agent contains a specific phenolic curing agent, the thermal conductivity of the cured product tends to be further improved. Although this reason is not clear, it is estimated that the comparatively small molecular weight between crosslinking points contributes to thermal conductivity. The hydroxyl group equivalent of the specific phenolic curing agent is preferably 50 g/eq to 150 g/eq, more preferably 50 g/eq to 120 g/eq, even more preferably 60 g/eq to 110 eq, and 70 g/eq to 110 g/eq It is particularly preferred to be.

The hydroxyl group equivalent of the phenol curing agent is set to a value measured by a method according to JIS K 0070:1992.

When the phenol curing agent is a solid, its melting point or softening point is not particularly limited. The melting point or softening point of the phenol curing agent is preferably 50°C to 250°C, more preferably 65°C to 200°C, and even more preferably 80°C to 170°C.

The melting point or softening point of the phenol curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.

In the epoxy resin composition, the content ratio of the epoxy resin and the curing agent is 0.5 to the ratio of the equivalent number of functional groups of the curing agent to the equivalent number of epoxy groups of the epoxy resin (equivalent number of functional groups of the curing agent/equivalent number of the epoxy group), 0.5 to It is preferably set to be in the range of 2.0, more preferably set to be 0.7 to 1.5, and even more preferably set to be 0.8 to 1.3. When the ratio is 0.5 or more, curing of the epoxy resin becomes sufficient, and the heat resistance, moisture resistance, and electrical properties of the cured product tend to be excellent. Moreover, when the said ratio is 2.0 or less, the amount of the functional group of the hardening agent remaining in a cured resin is suppressed, and there exists a tendency for excellent electrical properties and moisture resistance.

[Inorganic filler]

The epoxy resin composition of the present disclosure contains an alumina particle, does not contain a silica particle, or contains an alumina particle and further contains silica particles in an amount of more than 0% by mass and 15% by mass or less with respect to the total amount of alumina particles and silica particles Contains fillers. The content of the inorganic filler is 75% by volume to 84% by volume relative to the total volume of the composition. The inorganic filler may contain inorganic fillers other than alumina particles and silica particles, may contain only alumina particles and silica particles, or may contain only alumina particles. Examples of the silica particles include spherical silica and crystalline silica.

The average particle diameter of the inorganic filler is not particularly limited. The average particle diameter of the inorganic filler is, for example, preferably 0.1 µm to 80 µm, and more preferably 0.3 µm to 50 µm. In the present disclosure, the average particle diameter of the inorganic filler refers to the average particle diameter of the alumina particles when the alumina particles are used alone as the inorganic filler, and the inorganic when the alumina particles and other inorganic fillers are used together as the inorganic filler It means the average particle diameter as a whole filler. When the average particle diameter of the inorganic filler is 0.1 µm or more, there is a tendency to easily suppress the increase in viscosity of the epoxy resin composition. When the average particle diameter of the inorganic filler is 80 µm or less, the mixing property of the epoxy resin composition and the inorganic filler is improved, and the state of the package obtained by curing tends to be more homogenous, so that the variation in properties tends to be suppressed. There is a tendency for the chargeability to improve. Incidentally, it is preferable that the distribution of the particle diameter of the inorganic filler has a maximum value in the range of 0.1 μm to 80 μm.

Among them, the average particle diameter of the alumina particles is, for example, preferably 0.1 μm to 80 μm, and more preferably 0.3 μm to 50 μm. When the average particle diameter of the alumina particles is 0.1 µm or more, there is a tendency to easily suppress the increase in viscosity of the epoxy resin composition. When the average particle diameter of the alumina particles is 80 µm or less, the mixing property of the epoxy resin composition and the alumina particles is improved, and the state of the package obtained by curing tends to be more homogenous, so that variation in properties tends to be suppressed. There is a tendency for the chargeability to improve.

Particularly, from the viewpoint of high thermal conductivity, the average particle diameter of the alumina particles is preferably 1 μm to 50 μm, and more preferably 2 μm to 30 μm. Especially, when the average particle diameter of alumina particles is 10 micrometers or more, there exists a tendency which is excellent in thermal conductivity. This is considered to be because the heat conduction path is likely to be formed.

In addition, when the inorganic filler contains silica particles, the average particle diameter of the silica particles is, for example, preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm, and 0.5 μm to 20 μm. It is more preferable. Especially, when the average particle diameter of the silica particles is 10 µm or more, there is a tendency to suppress warpage of the package when cured. When the average particle diameter of the silica particles is 50 µm or less, the fluidity tends to be improved.

In the present disclosure, the average particle diameter of the inorganic filler can be measured using a dry particle size distribution meter or a wet particle size distribution measuring device in the state of a slurry in which the inorganic filler is dispersed in water or an organic solvent. Particularly in the case of containing particles of 1 µm or less, it is preferable to measure using a wet particle size distribution meter. Specifically, the water slurry in which the concentration of the inorganic filler was adjusted to about 0.01% by mass was treated with a bath ultrasonic cleaner for 5 minutes, and a laser diffraction particle size measuring device (LA-960, Horiba Seisakusho, Ltd.) was used. It can be obtained from the average value of all the particles detected. In the present disclosure, the average particle diameter indicates the particle diameter (D50) when the cumulative from the small diameter side becomes 50% in the volume-based particle size distribution.

In one embodiment, from the viewpoint of thermal conductivity, it is preferable to use alumina particles having an average particle diameter of 1 μm or more and alumina particles having an average particle diameter of less than 1 μm in combination. For example, alumina particles having an average particle diameter of 1 μm to 50 μm and alumina particles having an average particle diameter of 0.1 μm or more and less than 1 μm are preferably used in combination, and alumina particles having an average particle diameter of 5 μm to 50 μm It is more preferable to use a combination of alumina particles having an average particle diameter of 0.1 μm or more and less than 1 μm, and alumina particles having an average particle diameter of 5 μm to 30 μm and alumina particles having an average particle diameter of 0.3 μm or more and less than 1 μm. It is more preferred to use.

In addition, when the inorganic filler further contains silica particles, from the viewpoint of fluidity, it is preferable to use silica particles having an average particle diameter of 1 µm or less in combination. For example, it is preferable to use a combination of silica particles having an average particle diameter of 0.1 μm to 1 μm, more preferably to use a combination of silica particles having an average particle diameter of 0.2 μm to 1 μm, and an average particle diameter It is more preferable to use the silica particles of 0.3 µm to 1 µm in combination.

It can be confirmed, for example, that the epoxy resin composition contains the inorganic filler combined as described above by obtaining a particle size distribution (frequency distribution) based on the volume of the inorganic filler.

The mixing ratio in the case where alumina particles having an average particle diameter of 1 µm or more and alumina particles having an average particle diameter of less than 1 µm are used in combination is not particularly limited. For example, it is preferable to blend so that the proportion of alumina particles having an average particle diameter of 1 µm or less is 5% by mass to 20% by mass relative to the total amount of alumina particles, and 10% by mass to 15% by mass It is more preferable.

From the viewpoint of fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical, and the particle size distribution of the inorganic filler is preferably widely distributed. For example, it is preferable that 70 mass% or more of the inorganic filler is spherical particles, and the particle diameter of the spherical particles is broadly distributed from 0.1 µm to 80 µm. Since such an inorganic filler easily forms a close-packed structure by mixing particles of different sizes, the increase in the viscosity of the epoxy resin composition is suppressed even when the content of the inorganic filler is increased, and an epoxy resin composition excellent in fluidity tends to be obtained.

The content of the inorganic filler is 75% by volume to 84% by volume relative to the total volume of the composition, and from the viewpoint of the balance of properties such as thermal conductivity and fluidity, it is preferably 76% by volume to 84% by volume, and 77% by volume to 83% It is more preferable that it is volume%.

The content of the inorganic filler is preferably 90% by mass to 96% by mass, and more preferably 91% by mass to 95% by mass with respect to the total mass of the composition, from the viewpoint of the balance of properties such as thermal conductivity and fluidity. , It is more preferable that it is 92 mass% to 94 mass%.

The inorganic filler contains alumina particles and does not contain silica particles, or alumina particles, and further contains silica particles in an amount of more than 0 mass% and 15 mass% or less with respect to the total amount of alumina particles and silica particles. From the viewpoint of thermal conductivity and fluidity, the inorganic filler contains alumina particles and does not contain silica particles, or alumina particles and further contains silica particles in an amount greater than 0% by mass and less than 10% by mass relative to the total amount of alumina particles and silica particles It is desirable to do. For example, even if the inorganic filler contains alumina particles and does not contain silica particles, or contains alumina particles and further contains silica particles in an amount of more than 0% by mass and 5% by mass or less based on the total amount of alumina particles and silica particles do. In addition, the inorganic filler may contain alumina particles and further contain silica particles in an amount of 5% to 10% by mass relative to the total amount of alumina particles and silica particles. When silica particles are used in combination with alumina particles, fluidity tends to be improved. Although this reason is not clear, it is speculated that the contact area between alumina particles decreases and friction between alumina particles decreases.

The inorganic filler other than the alumina particles and silica particles is not particularly limited, and is not particularly limited, and includes glass, calcium carbonate, zirconium silicate, magnesium oxide, calcium silicate, silicon nitride, aluminum nitride, boron nitride, silicon carbide, industrial diamond, beryllia, zirconia, and zircon. , Particles of inorganic substances such as forsterite, steatite, spinel, mullite, titania, talc, clay, and mica, and beads in which these particles are spheroidized. In addition, an inorganic filler having a flame retardant effect may be used. Examples of the inorganic filler having a flame retardant effect include particles such as aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium and zinc composite hydroxides, and zinc borate. Inorganic fillers other than alumina particles and silica particles may be used alone or in combination of two or more.

The content ratio of inorganic fillers other than alumina particles and silica particles relative to the total volume of the inorganic filler is preferably 20% by volume or less, more preferably 10% by volume or less, still more preferably 5% by volume or less, and 2% by volume It is particularly preferable that the following.

The porosity of the inorganic filler is not particularly limited, preferably 18 volume% or less, more preferably 16 volume% or less, further preferably 15 volume% or less, and particularly preferably 14 volume% or less. The porosity of the inorganic filler may be 7% by volume or more. When the inorganic filler is one type, the porosity of the inorganic filler means the porosity of one inorganic filler, and when the inorganic filler is two or more, the porosity of the inorganic filler is the porosity of a mixture of two or more types of inorganic fillers Means

The porosity of the inorganic filler is a value indicating the ratio of the voids ((bulk/bulk volume of the inorganic filler) x 100 (%)) to the bulk volume of the inorganic filler. When the weight of the inorganic filler is the same, the bulk volume of the inorganic filler decreases as the porosity decreases. When the bulk volume of the inorganic filler contained in the epoxy resin composition decreases, even if the content of the inorganic filler contained in the epoxy resin composition is the same, the value obtained by subtracting the bulk volume of the inorganic filler from the volume of the epoxy resin composition increases. Hereinafter, this value may be called "amount of surplus resin." When the porosity of the inorganic filler decreases (i.e., the amount of surplus resin increases), the curability, fluidity, moldability of the epoxy resin composition, and the thermal conductivity of the cured product tend to improve. Although this reason is not clear, it is thought that the viscosity of an epoxy resin composition is reduced and fluidity|liquidity improves by increasing the amount of surplus resin. In addition, it is presumed that by increasing the amount of the surplus resin, the dispersibility at the time of kneading the epoxy resin composition is improved, and the curability, moldability, and thermal conductivity of the cured product are improved.

The porosity of the inorganic filler refers to a value measured by the following method.

The epoxy resin composition is put in a crucible, left at 800°C for 4 hours, and painted. The particle size distribution of the obtained ash is measured by applying a refractive index of alumina using a laser diffraction particle size distribution system (for example, Horiba Seisakusho, LA920). From the particle size distribution, the porosity ε is calculated using the following Ouchiyama equation. Incidentally, the Ouchiyama food is described in detail in the following documents.

N. Ouchiyama and T. Tanaka, Ind. Eng. Chem. Fundam., 19, 338 (1980)

N. Ouchiyama and T. Tanaka, Ind. Eng. Chem. Fundam., 20, 66 (1981)

N. Ouchiyama and T. Tanaka, Ind. Eng. Chem. Fundam., 23, 490 (1984)

The particle size distribution of the inorganic filler is not particularly limited. For example, in the particle size distribution based on the volume of the inorganic filler, the proportion of particles having a particle diameter of 1 µm or less is 9% by volume or more, and the proportion of particles having a particle diameter of 1 µm or more and 10 µm or less is 45 volume% or less. , The proportion of particles having a particle diameter of more than 10 µm to 30 µm is 20% by volume or more, and the proportion of particles having a particle diameter of more than 30 µm is preferably 18% by volume or more. When the inorganic filler exhibiting such a specific particle size distribution is contained, it is excellent in curability, fluidity, and moldability, and tends to be excellent in thermal conductivity when used as a cured product.

In the particle size distribution based on the volume of the inorganic filler, the proportion of particles having a particle diameter of 1 µm or less is 11% by volume or more, and the proportion of particles having a particle diameter of more than 1 µm and 10 µm or less is 40% by volume or less, and the particle diameter It is more preferable that the proportion of particles having a size of 10 µm or more and 30 µm or less is 22% by volume or more, and the proportion of particles having a particle diameter of 30 µm or more is 20% by volume or more.

In the particle size distribution based on the volume of the inorganic filler, the proportion of particles having a particle diameter of 1 µm or less is 12% by volume or more, and the proportion of particles having a particle diameter of 1 µm or more and 10 µm or less is 30% by volume or less, and the particle diameter is It is more preferable that the proportion of particles having a size of 10 µm or more and 30 µm or less is 24% by volume or more, and the proportion of particles having a particle diameter of 30 µm or more is 30% by volume or more.

In the particle size distribution based on the volume of the inorganic filler, the proportion of particles having a particle diameter of 1 µm or less is 20% by volume or less, and the proportion of particles having a particle diameter of 1 µm or more and 10 µm or less is 15% by volume or more, and the particle diameter The proportion of particles having a size of 10 µm or more and 30 µm or less is 35% by volume or less, and the proportion of particles having a particle diameter of 30 µm or more may be 45% by volume or less.

The particle size distribution based on the volume of the inorganic filler can be measured by the following method.

To the solvent (pure water), the inorganic filler to be measured is added together with 1 mass% to 8 mass% of surfactant within a range of 1 mass% to 5 mass%, and vibrated for 30 seconds to 5 minutes with a 110 W ultrasonic cleaner, Disperse the inorganic filler. About 3 mL of the dispersion is injected into the measuring cell and measured at 25°C. The measurement device measures a volume-based particle size distribution using a laser diffraction particle size distribution system (for example, Horiba Seisakusho, LA920). The average particle diameter is determined as the particle diameter (D50%) when the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution. Incidentally, the refractive index uses the refractive index of the alumina particles. In the case where the inorganic filler is a mixture of alumina particles and other inorganic fillers, it is assumed that the refractive index uses the refractive index of the alumina particles.

The method for adjusting the particle size distribution of the inorganic filler is not particularly limited. For example, a small particle diameter inorganic filler having an average particle diameter of about 0.5 µm, a medium particle diameter inorganic filler having an average particle diameter of about 2 µm, and an inorganic filler having a large particle diameter having an average particle diameter of about 45 µm are appropriately combined. You may prepare an inorganic filler showing the particle size distribution based on the volume exemplified above.

[Plasticizer]

The epoxy resin composition contains a plasticizer. When the epoxy resin composition contains a plasticizer, even if the inorganic filler containing alumina particles is highly charged, there is a tendency to suppress the occurrence of wire flow or the like. This reason is presumed to be attributable to a decrease in the high temperature elastic modulus and an improvement in fluidity. Examples of the plasticizer include organic phosphorus compounds such as triphenylphosphine oxide and phosphoric acid ester, silicones, and modified compounds thereof. Moreover, an indene-styrene copolymer is also suitably used as a plasticizer. Especially, it is preferable that a plasticizer contains an organic phosphorus compound, and it is more preferable to contain a triphenylphosphine oxide. The content rate of the plasticizer is preferably 0.001% by mass to 30% by mass relative to the epoxy resin, more preferably 5% by mass to 20% by mass, and even more preferably 5% by mass to 15% by mass. The plasticizer may be used alone or in combination of two or more.

[Curing accelerator]

The epoxy resin composition of the present disclosure may contain a curing accelerator as necessary. As a hardening accelerator, what is normally used for the sealing epoxy resin composition can be used selecting suitably. Examples of the curing accelerator include organophosphorus compounds, imidazole compounds, tertiary amines and quaternary ammonium salts. Especially, an organophosphorus compound is preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of the organic phosphorus compound include organic phosphines such as tributylphosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, methyldiphenylphosphine, and triparatolylphosphine, and maleic anhydride to these phosphines, Phosphorus compounds having an intramolecular polarization formed by adding a compound having a π bond such as benzoquinone or diazophenylmethane (for example, an adduct of triphenylphosphine and benzoquinone and triparatolylphosphine and benzoquinone Adducts); Tetraphenylphosphoniumtetraphenylborate, triphenylphosphinetetraphenylborate, 2-ethyl-4-methylimidazoletetraphenylborate, triphenylphosphonium-triphenylborane, and the like. When an organophosphorus compound is used as a curing accelerator, high reliability tends to be obtained in an electronic component device sealed using an epoxy resin composition. Although this reason is not clear, it can think as follows. In general, when the epoxy resin composition contains alumina particles, since the curability decreases, there is a tendency to increase the amount of the curing accelerator. However, when the curing accelerator is increased, the amount of chlorine ions generated by the reaction of the chlorine derived from epichlorohydrin, which is a raw material of the epoxy resin, and the curing accelerator increases, which may lower the reliability of the electronic component device. On the other hand, since the organophosphorus compound is not too high in reactivity, the use of the organophosphorus compound as a curing accelerator suppresses the reaction with chlorine, so generation of chlorine ions is also suppressed, and it is thought that the decrease in reliability can be suppressed. do.

When the epoxy resin composition contains a curing accelerator, the content of the curing accelerator is not particularly limited. For example, it is preferably 1.0 mass% to 10 mass%, and 1.5 mass% to 7 mass% with respect to the total amount of the epoxy resin and the curing agent. It is more preferable that it is %, and it is still more preferable that it is 1.8 mass%-6 mass %.

[Organic solvent]

The epoxy resin composition of the present disclosure may contain an organic solvent. When the epoxy resin composition contains an organic solvent, the viscosity of the composition decreases, and kneadability and fluidity tend to improve. The organic solvent is not particularly limited and may contain, for example, an organic solvent having a boiling point of 50°C to 100°C (hereinafter also referred to as a specific organic solvent).

The specific organic solvent is not particularly limited, and for example, it has a boiling point of 50°C to 100°C, and preferably can be used by appropriately selecting those that are non-reactive with components in the epoxy resin composition. Examples of specific organic solvents include alcohol solvents, ether solvents, ketone solvents, and ester solvents. Among them, alcohol-based solvents are preferred, and methanol (boiling point 64.7°C), ethanol (boiling point 78.37°C), propanol (boiling point 97°C) and isopropanol (boiling point 82.6°C) are more preferable. Specific organic solvents may be used alone or in combination of two or more. Incidentally, the specific organic solvent may be added when the epoxy resin composition is produced, or may be generated in the reaction of the kneading process when the epoxy resin composition is produced. Incidentally, in the present disclosure, the boiling point of a specific organic solvent refers to the boiling point of a specific organic solvent measured at normal pressure.

The content rate of the specific organic solvent in the epoxy resin composition is not particularly limited. It is preferable that the content rate of a specific organic solvent is 0.1 mass%-10 mass% with respect to the total mass of an epoxy resin composition, for example, It is more preferable that it is 0.3 mass%-4.0 mass% from a viewpoint of further improving thermal conductivity. It is more preferable that it is 0.3 mass%-3.0 mass %, and it is especially preferable that it is 0.3 mass%-2.5 mass %. When the content rate of a specific organic solvent is 0.3 mass% or more, the effect of improving fluidity tends to be higher. When the content ratio of the specific organic solvent is 3.0% by mass or less, generation of voids is more suppressed when curing the epoxy resin in the epoxy resin composition, and the decrease in insulation reliability tends to be further suppressed.

The content rate of the alcohol-based solvent in the specific organic solvent is not particularly limited. The content of the alcohol-based solvent is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 90% by mass or more, and particularly 95% by mass or more with respect to the total mass of the specific organic solvent. desirable. Moreover, it is not necessary for the epoxy resin composition to contain substantially any specific organic solvent other than the alcohol-based solvent.

[additive]

The epoxy resin composition may contain additives such as an anion exchanger, a release agent, a flame retardant, a coupling agent, a stress reliever, and a colorant, if necessary.

(Anion exchanger)

The epoxy resin composition may contain an anion exchanger as needed. Particularly, when an epoxy resin composition is used as a sealing material, it is preferable to contain an anion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device having the element to be sealed.

The anion exchanger is not particularly limited and can be selected from those conventionally used in the art. For example, hydrotalcite compounds and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth are mentioned.

The anion exchanger is not particularly limited and can be selected from those conventionally used in the art. Examples of the anion exchanger include hydrotalcite compounds having a composition represented by the following formula (I), and hydrous oxides of elements selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony. The anion exchanger may be used alone or in combination of two or more.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _x/ 2mH ₂ O (I)

(0<X≤0.5, m is positive number)

The hydrotalcite compound is a compound having a property of capturing an anion such as a halogen ion by substituting with CO ₃ in the structure, and the halogen ion introduced into the crystal structure does not desorb until the crystal structure is destroyed at about 350° C. or higher. . Examples of the hydrotalcite having such properties include Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ·4H ₂ O produced as a natural product, and Mg _4.3 Al ₂ (OH) _12.6 CO ₃ ·mH ₂ O as a synthetic product. .

When the epoxy resin composition contains a phenolic curing agent as a curing agent, the epoxy resin composition is acidic under the influence of the phenolic curing agent (for example, the extract of the cured product using pure water becomes pH 3 to 5). In this case, for example, aluminum, which is an amphoteric metal, is an environment that is susceptible to corrosion by the epoxy resin composition, but the corrosion of aluminum is suppressed by the epoxy resin composition containing a hydrotalcite compound also having an action of adsorbing acid. Tend to

In addition, hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth, and antimony can also be captured by substituting hydroxide ions for anions such as halogen ions. In addition, these ion exchangers exhibit excellent ion exchange ability on the acid side. Therefore, when the epoxy resin composition contains these ion exchangers, corrosion of aluminum tends to be suppressed, as in the case of containing a hydrotalcite compound. Examples of the hydrous oxide include MgO·nH ₂ O, Al ₂ O ₃ ·nH ₂ O, ZrO ₂ ·H ₂ O, Bi ₂ O ₃ ·H ₂ O, Sb ₂ O ₅ ·nH ₂ O, and the like.

When the epoxy resin composition contains an anion exchanger, the content rate of the anion exchanger is not particularly limited as long as it is an amount sufficient to capture anions such as halogen ions. When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger is preferably 0.1% by mass to 30% by mass, and more preferably 1.0% by mass to 5% by mass.

(Release agent)

The epoxy resin composition may contain a mold release agent as necessary from the viewpoint of exerting good mold release properties to the mold in the molding step. The type of the release agent is not particularly limited, and examples of the release agent known in the art. Specifically, examples of the release agent include ester fatty acid waxes such as carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-polyethylene oxide. Among them, carnauba wax and polyolefin wax are preferred. The mold release agent may be used alone or in combination of two or more.

As the polyolefin-based wax, commercially available products may be used, and, for example, low-molecular-weight polyethylene having a number average molecular weight of about 500 to 10000, such as H4's H4, PE, and PED series.

When the epoxy resin composition contains a polyolefin-based wax, the content rate of the polyolefin-based wax is preferably 0.01% by mass to 10% by mass relative to the epoxy resin, and more preferably 0.10% by mass to 5% by mass. When the content ratio of the polyolefin wax is 0.01% by mass or more, sufficient release property tends to be obtained, and when it is 10% by mass or less, sufficient adhesiveness tends to be obtained.

In addition, when the epoxy resin composition contains other release agents other than polyolefin-based wax, or when the epoxy resin composition contains polyolefin-based wax and other release agents, the content rate of other release agents other than polyolefin-based wax is 0.1 relative to the epoxy resin. It is preferable that it is mass% to 10 mass %, and it is more preferable that it is 0.5 mass% to 3 mass %.

(Flame retardant)

From the viewpoint of imparting flame retardancy, the epoxy resin composition may contain a flame retardant as necessary. The flame retardant is not particularly limited, and examples thereof include known organic and inorganic compounds including halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides, and acenaphthylene. The flame retardant may be used alone or in combination of two or more.

When the epoxy resin composition contains a flame retardant, the content of the flame retardant is not particularly limited as long as the flame retardant effect is obtained. When the epoxy resin composition contains a flame retardant, the content of the flame retardant is preferably 1% by mass to 30% by mass relative to the epoxy resin, and more preferably 2% by mass to 15% by mass.

(Coupling agent)

The epoxy resin composition may contain a coupling agent from the viewpoint of increasing the adhesion between the resin component and the inorganic filler, if necessary. The type of coupling agent is not particularly limited. Examples of the coupling agent include various silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, methacrylsilane, acrylicsilane, and vinylsilane, titanium compounds, aluminum chelate compounds, and aluminum and zirconium-containing compounds. Can. The coupling agent may be used alone or in combination of two or more.

When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably 0.05% by mass to 5.0% by mass relative to the inorganic filler, and more preferably 0.10% by mass to 2.5% by mass. When the content rate of the coupling agent is 0.05 mass% or more, the adhesiveness with the frame tends to be improved, and if it is 5.0 mass% or less, the moldability of the package tends to be excellent.

(Stress reliever)

The epoxy resin composition may contain a stress relieving agent such as silicone oil and silicone rubber particles, if necessary, from the viewpoint of reducing the amount of warpage deformation and the package crack of the package. As a usable stress reliever, a flexible agent (stress reliever) generally used in the art can be appropriately selected and used.

Specific examples of the stress reliever include thermoplastic elastomers such as silicone, polystyrene, polyolefin, polyurethane, polyester, polyether, polyamide, and polybutadiene; Rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder; And rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicon copolymer, and methyl methacrylate-butyl acrylate copolymer. Among them, a silicon-based stress reliever containing silicon is preferred. Examples of the silicone stress reliever include an epoxy group, an amino group, and polyether-modified ones. The stress reliever may be used alone or in combination of two or more.

(coloring agent)

The epoxy resin composition may contain colorants such as carbon black, fibrous carbon, organic dyes, organic colorants, titanium oxide, podium, and bengala. When the epoxy resin composition contains a colorant, the content of the colorant is preferably 0.05% by mass to 5.0% by mass relative to the inorganic filler, and more preferably 0.10% by mass to 2.5% by mass.

[Preparation method of epoxy resin composition]

Any method may be used in the preparation of the epoxy resin composition as long as various components can be dispersed and mixed. As a general method, after sufficiently mixing various components with a mixer or the like, a method of melt-kneading with a mixing roll, an extruder, or the like, cooling, and pulverizing may be mentioned. More specifically, the epoxy resin composition, for example, by mixing and stirring the above-mentioned components, kneaded in a kneader, roll, extruder, etc. previously heated to 70°C to 140°C, cooled, crushed, etc. It can be obtained by a method. The epoxy resin composition may be tabletted to dimensions and masses suitable for the molding conditions of the package. By tableting the epoxy resin composition, handling becomes easy.

[Flowability of epoxy resin composition]

When the fluidity is measured by the following method, the epoxy resin composition of the present disclosure preferably exhibits a flow distance of 100 cm or more. The epoxy resin composition is molded using a spiral flow measuring mold according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition is measured. The epoxy resin composition is molded using a transfer molding machine under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds.

<Epoxy resin cured product>

The cured epoxy resin of the present disclosure is obtained by curing the above-described epoxy resin composition. Since the cured epoxy resin of the present disclosure is obtained by curing the above-mentioned epoxy resin composition, it tends to be excellent in thermal conductivity.

[The thermal conductivity of cured epoxy resin]

The thermal conductivity of the cured epoxy resin is not particularly limited, and is preferably 4 W/(m·K) or more. In the present disclosure, the thermal conductivity of the cured epoxy resin product is taken as the following measurement. Using the epoxy resin composition, transfer molding is performed under conditions of a mold temperature of 180°C, a molding pressure of 7 MPa, and a curing time of 300 seconds to obtain a molded epoxy resin cured product. The specific gravity of the obtained cured epoxy resin is measured by the Archimedes method, and the specific heat is measured by DSC (eg, Perkin Elmer, DSC Pyris1). In addition, the thermal diffusivity of the obtained cured product is measured by a laser flash method using a thermal diffusivity measuring device (for example, NETZSCH, LFA467). The obtained specific gravity, specific heat and thermal diffusivity are used to calculate the thermal conductivity of the cured epoxy resin.

<Electronic component device>

The electronic component device of the present disclosure has an element and a cured product of the epoxy resin composition of the present disclosure sealing the device, and has the form of a BGA package. The BGA package is manufactured by mounting an element on the surface of a substrate on which a metal bump is formed on the back surface, connecting the element and wiring formed on the substrate by bump or wire bonding, and sealing the element. Examples of the substrate include glass-epoxy substrates and printed wiring boards. Examples of the element include an active element and a passive element. Examples of active elements include semiconductor chips, transistors, diodes, and thyristors. As a passive element, a capacitor, a resistor, a coil, etc. are mentioned.

In the electronic component device of the present disclosure, the method for sealing the element with a cured epoxy resin is not particularly limited, and it is possible to apply a method known in the art. For example, a low pressure transfer molding method is common, but an injection molding method, compression molding method, or the like may be used.

Example

Hereinafter, although an example of the said embodiment is demonstrated concretely by an Example, this invention is not limited to these Examples.

(Preparation of epoxy resin composition)

The components shown below were mixed at a blending ratio shown in Table 1 to prepare epoxy resin compositions of Examples and Comparative Examples. In Table 1, when the compounding quantity of a component is not specifically described, it represents parts by mass, and "-" indicates that the component is not blended.

·Epoxy resin 1… Biphenyl type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name "YX-4000")

·Epoxy resin 2… Bisphenol F type epoxy resin (Shinnitetsu Sumikin Chemical Co., Ltd., trade name ``YSLV-80XY'')

·Hardeners... Polyfunctional phenolic resin (Air Water Co., Ltd., trade name "HE910", triphenylmethane type phenolic resin having a hydroxyl equivalent of 105 g/eq)

·Curing accelerator… Phosphorus hardening accelerator (organic phosphorus compound)

The following was prepared as an inorganic filler.

Inorganic filler 1: alumina-silica mixed filler (silica content: 10% by mass), volume average particle diameter: 10 µm

Inorganic filler 2: alumina filler, volume average particle diameter: 10 µm

Inorganic filler 3: alumina filler, volume average particle diameter: 0.8 µm

Inorganic filler 4: silica filler, volume average particle diameter: 0.8 µm

The following were prepared as a plasticizer.

Plasticizer 1: Organic phosphine oxide

Plasticizer 2: Inden-styrene copolymer (Nitto Chemical Co., Ltd., NH-100S)

In addition, the following were prepared as various additives.

Coupling agent: Anilinosilane (N-phenyl-3-aminopropyl trimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name: KBM-573)

Colorant: Carbon black (Mitsubishi Chemical Co., Ltd., trade name: MA-100)

· Release agent: Montan acid ester (NODA, Cerarica Co., Ltd.)

(Evaluation of liquidity)

The fluidity evaluation of the epoxy resin composition was performed by a spiral flow test.

Specifically, the epoxy resin composition was molded using a spiral flow measuring mold according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition was measured. The epoxy resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds. In addition, fluidity was set to A of 100 cm or more and B of less than 100 cm.

(Evaluation of thermal conductivity)

Evaluation of the thermal conductivity when the epoxy resin composition was cured was performed as follows. Specifically, using the prepared epoxy resin composition, transfer molding was performed under conditions of a mold temperature of 180°C, a molding pressure of 7 MPa, and a curing time of 300 seconds to obtain a mold-shaped cured product. The obtained cured product had a specific gravity of 3.00 to 3.40 measured by the Archimedes method. The specific heat of the obtained cured product was measured by DSC (Perkin Elmer, DSC Pyris1). In addition, the thermal diffusivity of the cured product was measured by a laser flash method using a thermal diffusivity measuring device (NETZSCH, LFA467). The thermal conductivity of the cured epoxy resin was calculated using the obtained specific gravity, specific heat and thermal diffusivity. The thermal conductivity was 4 W/(m·K) or more, and A was less than 4 W/(m·K).

In other words, when the content of the inorganic filler in the composition in Example 6 was changed to 85% by mass, kneading was performed, and a kneaded product could not be obtained.

As can be seen from Table 2, the epoxy resin 2, a curing agent, an inorganic filler and a plasticizer, the content of the inorganic filler is 75% by volume to 84% by volume, and the ratio of silica particles to the total amount of alumina particles and silica particles In Examples 1 to 8, which were within the range of 0% by mass to 15% by mass, all evaluations of fluidity and thermal conductivity were good.

As for the indication of the Japanese patent application 2017-254882, the whole is taken in into this specification by reference.

All documents, patent applications, and technical specifications described in this specification are incorporated into and incorporated in the present specification to the same extent that individual documents, patent applications, and technical specifications are incorporated by reference, and to the same extent as described individually.

Claims (11)

An epoxy resin containing a bisphenol F-type epoxy resin,
Hardener,
An inorganic filler comprising alumina particles and no silica particles, or containing alumina particles and further comprising silica particles in an amount greater than 0% by mass and not more than 15% by mass relative to the total amount of alumina particles and silica particles,
Plasticizer
Containing, the content of the inorganic filler is 75% by volume to 84% by volume,
Epoxy resin composition for sealing a ball grid array package. The epoxy resin composition for sealing a ball grid array package of claim 1, wherein the epoxy resin further comprises a biphenyl-type epoxy resin. The inorganic filler according to claim 1 or 2, wherein the inorganic filler contains alumina particles and does not contain silica particles, or contains alumina particles and further contains silica particles in an amount greater than 0% by mass relative to the total amount of alumina particles and silica particles. An epoxy resin composition for sealing a ball grid array package containing 10% by mass or less. The epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 3, wherein the curing agent includes a hydroxyl group equivalent of 150 g/eq or less of a phenol curing agent. The epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 4, wherein the curing agent comprises a phenol resin having three or more phenolic hydroxyl groups in one molecule. The epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 5, wherein the curing agent comprises a triphenylmethane type phenol resin. The epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 6, wherein the porosity of the inorganic filler is 18 vol% or less. The proportion of particles having a particle diameter of 1 µm or less in a volume-based particle size distribution of the inorganic filler according to any one of claims 1 to 7, wherein the particle diameter exceeds 10 µm. A ball grid in which the proportion of particles having a size of µm or less is 45% by volume or less, the proportion of particles having a particle diameter of more than 10 µm and 30 µm or less is 20% by volume or more, and the proportion of particles having a particle diameter of 30 µm or more is 18% by volume or more. Epoxy resin composition for sealing an array package. The proportion of particles having a particle diameter of 1 µm or less in an amount of 11 vol% or more, and a proportion of particles having a particle diameter in excess of 1 µm and 10 µm or less in 40 volumes in the particle size distribution based on the volume of the inorganic filler according to claim 8, is 40 volumes. %, the proportion of particles having a particle diameter of more than 10 μm and 30 μm or less is 22% by volume or more, and the proportion of particles having a particle diameter of more than 30 μm is 20% by volume or more. The epoxy resin composition for sealing a ball grid array package. The cured epoxy resin obtained by curing the epoxy resin composition for sealing the ball grid array package according to any one of claims 1 to 9. An electronic component device comprising an element and the cured epoxy resin according to claim 10 that seals the element and has the form of a ball grid array package.