JP2020066697A - Liquid resin composition and electronic component device and method for producing the same - Google Patents

Abstract

To provide a liquid resin composition having excellent filling properties.SOLUTION: A liquid resin composition contains (A) an epoxy resin, (B) a curing agent, (C) first silica particles, each of which is surface-treated with a silane coupling agent having an epoxy group, and which has an average particle size of 5 nm or more to less than 200 nm, and (D) second silica particles with an average particle size of 0.2-5 μm. The total content of the (C) first silica particles and the (D) second silica particles is 40-80 mass%. The ratio in mass between the (C) first silica particles and the (D) second silica particles ((D) second silica particles/(C) first silica particles) is 2-10.SELECTED DRAWING: None

Description

  The present invention relates to a liquid resin composition, an electronic component device, and a method for manufacturing the same.

  Conventionally, in the field of element encapsulation of electronic component devices such as transistors and ICs (Integrated Circuits), resin encapsulation has been the mainstream in terms of productivity, cost, etc., and various types of resin compositions have been applied. . Among them, epoxy resins are widely used because they have various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness with inserts. In a semiconductor device mounted with bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package), a liquid resin composition for electronic components is widely used as an encapsulating material. Further, in a semiconductor device (flip chip) in which a semiconductor element is directly bump-connected on a wiring board having a substrate made of ceramic, glass / epoxy resin, glass / imide resin, polyimide film, etc., the bump-connected semiconductor element and wiring board The liquid resin composition for electronic parts is used as an underfill material for filling the gap. These liquid resin compositions for electronic parts play an important role in protecting electronic parts from temperature and humidity, mechanical external force and the like.

  For example, in order to provide a highly reliable (moisture resistance, thermal shock resistance) electronic component device including a sealing epoxy resin composition having excellent moisture resistance and low stress, and an element sealed by the same. , (A) Liquid epoxy resin, (B) Hardener containing liquid aromatic amine, (C) Rubber particles, (D) Epoxy resin composition for encapsulation containing inorganic filler, and encapsulation thereof An electronic component device including an element sealed with an epoxy resin composition is disclosed (see, for example, Patent Document 1).

JP-A-2001-270976

  However, semiconductors have made remarkable progress, and in the flip-chip method for bump connection, the bump pitch and bump height have become smaller as the number of bumps has increased, resulting in a narrower gap. As semiconductors become highly integrated, the chip size also increases, and underfill materials are required to have characteristics of uniformly filling large-area voids with a narrow gap.

  One form of the present invention has been made in view of the above conventional circumstances, and an object of the present invention is to provide a liquid resin composition having excellent filling properties, an electronic component device sealed by the liquid resin composition, and a method for manufacturing the same.

The specific means for achieving the above object are as follows.
<1> (A) Epoxy resin, (B) Curing agent, (C) First silica particles having an average particle size of 5 nm or more and less than 200 nm, which are surface-treated with a silane coupling agent having an epoxy group, and (D) ) Including second silica particles having an average particle size of 0.2 μm to 5 μm,
The ratio of the total of the (C) first silica particles and the (D) second silica particles is 40% by mass to 80% by mass,
The mass-based ratio of the (C) first silica particles to the (D) second silica particles ((D) second silica particles / (C) first silica particles) is 2 to 10. Liquid resin composition.
<2> The liquid resin composition according to <1>, wherein the epoxy resin (A) has a viscosity at 25 ° C. of 1000 Pa · s or less.
<3> The liquid resin composition according to <1> or <2>, in which the (B) curing agent contains an amine curing agent.
<4> The liquid resin composition according to any one of <1> to <3>, which contains an ion trap agent.
<5> The liquid resin composition according to any one of <1> to <4>, which contains a curing accelerator.
<6> The liquid resin composition according to any one of <1> to <5>, which contains an antioxidant.
<7> The liquid resin composition according to any one of <1> to <6>, which has a volatile content of 5% by mass or less.
<8> A substrate having a circuit layer,
An electronic component disposed on the substrate and electrically connected to the circuit layer,
A cured product of the liquid resin composition according to any one of <1> to <7>, which is disposed in a gap between the substrate and the electronic component.
An electronic component device including.
<9> The liquid resin composition according to any one of <1> to <7>, including a substrate having a circuit layer and an electronic component arranged on the substrate and electrically connected to the circuit layer. A method for manufacturing an electronic component device, which includes a step of sealing with an object.

  According to one aspect of the present invention, it is possible to provide a liquid resin composition having excellent filling properties, an electronic component device sealed with the same, and a method for manufacturing the same.

Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present disclosure, the term “process” includes not only a process independent of other processes but also the process even if the process is not clearly distinguishable from other processes as long as the purpose of the process is achieved. .
In the present disclosure, the numerical range indicated by using "to" includes the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit or the lower limit described in one numerical range may be replaced with the upper limit or the lower limit of the numerical range described in other stages. . Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may include a plurality of types of corresponding substances. When multiple types of substances corresponding to each component are present in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified.
In the present disclosure, the term “layer” may be formed in a part of the region in addition to being formed in the whole region when the region in which the layer is present is observed. included.

<Liquid resin composition>
The liquid resin composition of the present disclosure is a first silica having an average particle size of 5 nm or more and less than 200 nm, which is surface-treated with (A) an epoxy resin, (B) a curing agent, and (C) a silane coupling agent having an epoxy group. Particles and (D) second silica particles having an average particle diameter of 0.2 μm to 5 μm, and the ratio of the total of the (C) first silica particles and the (D) second silica particles is , 40% by mass to 80% by mass, and the mass-based ratio of the (C) first silica particles and the (D) second silica particles ((D) second silica particles / (C) first). Silica particles) are 2-10.
The liquid resin composition of the present disclosure has excellent filling properties. The reason for this is not clear, but it is presumed as follows.
The silica particles having an average particle diameter of 5 nm or more and less than 200 nm are surface-treated with a silane coupling agent having an epoxy group, whereby the wettability between the silica particles and the epoxy resin is improved. Further, by combining silica particles having an average particle diameter of 5 nm or more and less than 200 nm and silica particles having an average particle diameter of 0.2 μm to 5 μm in a predetermined ratio, the fluidity of the silica particles as a whole is improved. For these reasons, the fluidity of the liquid resin composition is improved, and as a result, the viscosity of the liquid resin composition is reduced, and thus the liquid resin composition of the present disclosure is presumed to have excellent filling properties.

  Hereinafter, each component constituting the liquid resin composition will be described. The liquid resin composition of the present disclosure is (A) an epoxy resin, (B) a curing agent, and (C) a first silica having an average particle size of 5 nm or more and less than 200 nm which is surface-treated with a silane coupling agent having an epoxy group. Particles, and (D) second silica particles having an average particle diameter of 0.2 μm to 5 μm, and may contain other components as necessary.

-Epoxy resin-
The liquid resin composition of the present disclosure contains (A) an epoxy resin. The epoxy resin as the component (A) imparts curability and adhesiveness to the liquid resin composition, and imparts heat resistance and durability to the cured product of the liquid resin composition. The epoxy resin is preferably a liquid epoxy resin. In the present disclosure, a solid epoxy resin may be used together with the liquid epoxy resin.

The liquid epoxy resin means a liquid epoxy resin at room temperature (25 ° C). Specifically, at 25 ° C., it means that the viscosity measured by an E-type viscometer is 1000 Pa · s or less. Specifically, the viscosity is measured using an E-type viscometer EHD type (cone angle 3 °, cone diameter 28 mm), measurement temperature: 25 ° C., sample volume: 0.7 ml, and the number of revolutions is sampled with reference to the following. Set the value according to the assumed viscosity of and measure the value 1 minute after the start of measurement.
(1) When the assumed viscosity is 100 Pa · s to 1000 Pa · s: rotational speed 0.5 rpm / minute (2) When the assumed viscosity is less than 100 Pa · s: rotational speed 5 rpm / minute Further, solid The epoxy resin means a solid epoxy resin at room temperature (25 ° C.).

The type of epoxy resin is not particularly limited. As the epoxy resin, a naphthalene type epoxy resin; a diglycidyl ether type epoxy resin such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A; orthocresol novolac type epoxy resin, and phenols and aldehydes Epoxidized novolak resin with epoxides; glycidyl ester type epoxy resin obtained by reaction of polybasic acid such as phthalic acid and dimer acid with epichlorohydrin; amine compound such as diaminodiphenylmethane, isocyanuric acid and aminophenol Examples thereof include glycidyl amine type epoxy resins obtained by the reaction of with epichlorohydrin.
Examples of the epoxy resin include bifunctional aliphatic epoxy compounds having two epoxy groups in the molecule such as alkylene glycol diglycidyl ether, poly (alkylene glycol) diglycidyl ether, and alkenylene glycol diglycidyl ether.

From the viewpoint of viscosity adjustment, the epoxy equivalent of the epoxy resin is preferably 80 g / eq to 400 g / eq, more preferably 85 g / eq to 350 g / eq, and 90 g / eq to 320 g / eq. Is more preferable.
The epoxy equivalent of the epoxy resin is measured by dissolving the weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and tetraethylammonium bromide acetic acid solution, and potentiometrically titrating with a perchloric acid acetic acid standard solution. An indicator may be used for this titration.

A commercial item may be used as the epoxy resin. Specific examples of commercially available epoxy resins include amine type epoxy resin (product name: jER630) manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin (product name: YDF-8170C) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Nippon Steel & Sumikin Chemical Co., Ltd. Bisphenol A type epoxy resin (product name: YD-128), DIC Corporation naphthalene type epoxy resin (product name: HP-4032D), product name "Epogosei PT (general grade)" (Yokkaichi Gosei Co., Ltd., polytetramethylene glycol) And the number average molecular weight of 700 to 800). The epoxy resin is not limited to these specific examples. The epoxy resins may be used alone or in combination of two or more.
The content of the epoxy resin is not particularly limited, and is, for example, preferably 5% by mass to 35% by mass, and 7% by mass to 33% by mass as a ratio of the solid content of the liquid resin composition. It is more preferable that the amount is 10% by mass to 32% by mass.

-Curing agent-
The liquid resin composition of the present disclosure contains (B) a curing agent. The curing agent as the component (B) may be any one as long as it undergoes a polymerization reaction with the epoxy resin. If the liquid resin composition has fluidity at room temperature (25 ° C.), it may be liquid or solid. It is possible.
Examples of the curing agent include amine type curing agents, phenol type curing agents, acid anhydride type curing agents and the like. Among these, amine-based curing agents are preferable as the curing agent.

Examples of the amine-based curing agent include chain aliphatic amines, cycloaliphatic amines, aliphatic aromatic amines, aromatic amines, and the like. From the viewpoint of heat resistance and electric characteristics, aromatic amines are preferable, and aromatic ring It is more preferable that an amino group is directly bonded to, and the aromatic ring is an aromatic amine containing one or two aromatic rings in one molecule.
Specific examples of the amine curing agent include m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene. , 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole and other aromatic amine curing agents having one aromatic ring; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone , 4,4'-methylenebis (2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, Aromatic amine curing agent having two aromatic rings such as 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane; a hydrolytic condensate of an aromatic amine curing agent; Aromatic amine curing agents having a polyether structure such as tetramethylene oxide di-p-aminobenzoic acid ester and polytetramethylene oxide diparaaminobenzoate; condensation products of aromatic diamine and epichlorohydrin; aromatic diamine and styrene Reaction products with and the like.

  A commercially available product may be used as the amine curing agent. Specific examples of commercially available amine-based curing agents include amine curing agents manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard-AA), amine curing agents manufactured by Mitsubishi Chemical Co., Ltd. (product name: jER Cure (registered trademark) 113, product name). : JER Cure (registered trademark) W, etc., but the amine-based curing agent is not limited to these specific examples. The amine curing agents may be used alone or in combination of two or more.

  As the acid anhydride-based curing agent, phthalic anhydride, maleic anhydride, methylhymic acid anhydride, hymic acid anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, methyltetrahydro Phthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, Hydrogenated methyl nadic acid anhydride, obtained by Diels-Alder reaction from maleic anhydride and a diene compound, and trialkyltetrahydrophthalic anhydride having a plurality of alkyl groups, various cyclic acid anhydrides such as dodecenyl succinic anhydride can be mentioned. .

The phenol-based curing agent is selected from the group consisting of phenol compounds (eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A and bisphenol F) and naphthol compounds (eg, α-naphthol, β-naphthol and dihydroxynaphthalene). Resin and phenol aralkyl resin; Resin; and naphthol aralkyl resin.
As the curing agent, one type may be used alone, or two or more types may be used in combination.

  Equivalent number of functional groups of the curing agent (for example, amino group in case of amine type curing agent, phenolic hydroxyl group in case of phenol type curing agent, acid anhydride group in case of acid anhydride type curing agent) The ratio to the number of equivalents of epoxy resin (number of equivalents of curing agent / number of equivalents of epoxy resin) is preferably set in the range of 0.6 to 1.4, and set in the range of 0.7 to 1.3. Is more preferable, and it is further preferable to set it in the range of 0.8 to 1.2.

-Inorganic filler-
The liquid resin composition of the present disclosure comprises, as an inorganic filler, (C) first silica particles having an average particle size of 5 nm or more and less than 200 nm, which are surface-treated with a silane coupling agent having an epoxy group, and (D). The second silica particles having an average particle diameter of 0.2 μm to 5 μm are included.
Examples of the silica particles include colloidal silica, hydrophobic silica, spherical silica, and the like, and are amorphous spherical silica from the viewpoint of fluidity of the liquid resin composition, heat resistance of the cured product of the liquid resin composition, and the like. It is preferable.
As the amorphous spherical silica, amorphous spherical silica produced by the sol-gel method is also preferable in terms of particle size controllability and purity. As silica, a composition containing silica obtained by the production method described in JP-A-2007-197655 may be used.

The ratio of the total of the first silica particles and the second silica particles is 40% by mass to 80% by mass, preferably 45% by mass to 75% by mass, and 50% by mass to 70% by mass. Is more preferable.
The mass-based ratio of the first silica particles and the second silica particles (second silica particles / first silica particles) is 2 to 10, preferably 2 to 8, and 2 to 6. It is more preferable, and it is further preferable that it is 3 to 6.
The liquid resin composition of the present disclosure may include other inorganic fillers other than silica particles. Other inorganic fillers include alumina, zircon, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, boron nitride, aluminum nitride, beryllia, zirconia and the like. Further, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide and zinc borate.
The content of the other inorganic filler in the inorganic filler is preferably 10% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.

  When the total content of the silica particles in the liquid resin composition is the same, compared with the case of using only the second silica particles as the inorganic filler, the first silica particles together with the second silica particles. When used together, the viscosity of the liquid resin composition tends to be lowered. Therefore, the total content of silica particles tends to be increased without increasing the viscosity of the liquid resin composition. The thermal expansion coefficient of the cured product of the liquid resin composition decreases due to the increase in the total content of silica particles, and as a result, the reliability of the electronic component device sealed with the liquid resin composition tends to improve. is there.

  The average particle diameter of the first silica particles is 5 nm or more and less than 200 nm, preferably 10 nm to 100 nm, and more preferably 20 nm to 75 nm. When the average particle diameter of the first silica particles is 5 nm or more, the viscosity of the liquid resin composition is unlikely to increase and the fluidity tends to be less likely to occur. When the average particle size of the first silica particles is less than 200 nm, the viscosity of the liquid resin composition tends to be lowered.

The specific surface area of the first silica particles, from the viewpoint of ^fluidity, is preferably 20m ² / g~500m 2 / ^g, more preferably 50m ² / g~300m 2 / g.

  The first silica particles are surface-treated with a silane coupling agent having an epoxy group. Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxy. Examples thereof include silane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These compounds are commercially available from Shin-Etsu Chemical Co., Ltd., etc.

  The method of surface-treating the silica particles with the silane coupling agent having an epoxy group is not particularly limited, and a surface-treatment method usually used can be appropriately selected. For example, a method of adding a solution containing a silane coupling agent having an epoxy group to a slurry containing silica particles, stirring, and then separating the surface-treated silica particles by filtration or the like to dry, a silane having an epoxy group. Examples thereof include a method of spraying a coupling agent onto silica particles and drying.

  The surface treatment amount of the silane coupling agent having an epoxy group on the first silica particles is not particularly limited. The surface treatment amount of the silane coupling agent having an epoxy group with respect to the first silica particles is preferably 0.1% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass. , 0.5% to 2% by mass is more preferable.

A commercial item may be used as the first silica particles. Specific examples of commercial products of the first silica particles include inorganic fillers (product name: YA010C, YA050C, etc.) manufactured by Admatechs Co., Ltd., inorganic fillers (product name: Siqas 0.05 μm), manufactured by Sakai Chemical Industry Co., Ltd., etc. However, the first silica particles are not limited to these specific examples.
The first silica particles may be used alone or in combination of two or more.

The proportion of the first silica particles in the inorganic filler is preferably 0.3% by mass or more. Further, the proportion of the first silica particles in the inorganic filler is preferably 35% by mass or less. The proportion of the first silica particles in the inorganic filler is more preferably 0.3% by mass to 35% by mass, further preferably 0.5% by mass to 35% by mass. When the proportion of the first silica particles in the inorganic filler is within the above range, there is a tendency that a liquid resin composition capable of exhibiting a bleeding reducing effect and having excellent fluidity can be obtained.
In one aspect, the proportion of the first silica particles in the inorganic filler is preferably 10% by mass to 35% by mass, more preferably 12% by mass to 35% by mass, and 13% by mass to 35% by mass. It is more preferable that the content is mass%.

  The second silica particles impart heat cycle resistance, moisture resistance, insulation and the like to the cured product of the liquid resin composition, and reduce stress during curing of the liquid resin composition.

The average particle diameter of the second silica particles is 0.2 μm to 5 μm, preferably 0.2 μm to 3 μm, more preferably 0.3 μm to 1 μm, and 0.4 μm to 0.8 μm. It is more preferable that there is.
The specific surface area of the second silica particles, from the viewpoint of ^fluidity, is preferably 1m ² / g~30m 2 / ^g, more preferably 2m ² / g~20m 2 / g.

  The proportion of the second silica particles in the inorganic filler is preferably 60% by mass or more. Further, the proportion of the second silica particles in the inorganic filler is preferably 99.7% by mass or less. The proportion of the second silica particles in the inorganic filler is more preferably 60% by mass to 99.7% by mass, and further preferably 65% by mass to 99.5% by mass.

  The second silica particles may have an organic group derived from a manufacturing raw material. Examples of the organic group that the second silica particles may have include an alkyl group such as a methyl group and an ethyl group.

A commercial item may be used as the second silica particles. Specific examples of commercially available second silica particles include spherical silica (product name: SO-E2) manufactured by Admatechs Co., Ltd., spherical silica (product name: SE2200) manufactured by Admatechs Co., Ltd. The silica particles are not limited to these specific examples.
The second silica particles may be used alone or in combination of two or more.

The specific surface area (BET specific surface area) of the inorganic filler can be measured from the nitrogen adsorption capacity according to JIS Z 8830: 2013. As an evaluation device, QUANTACHROME company: AUTOSORB-1 (trade name) can be used. Since it is considered that the water adsorbed on the sample surface and structure influences the gas adsorption ability, it is preferable to first perform a pretreatment for removing water by heating when measuring the BET specific surface area. .
In the pretreatment, the measurement cell charged with 0.05 g of the measurement sample was depressurized to 10 Pa or less by a vacuum pump, heated at 110 ° C., held for 3 hours or more, and then kept at room temperature (vacuum). Cool naturally to 25 ° C. After performing this pretreatment, the evaluation temperature is set to 77K, and the evaluation pressure range is measured as relative pressure (equilibrium pressure to saturated vapor pressure) of less than 1.

The average particle size of the inorganic filler can be measured by the following method.
An inorganic filler to be measured is added to a solvent (pure water) together with a surfactant in an amount of 1% by mass to 8% by mass within a range of 1% by mass to 5% by mass, and the ultrasonic cleaner of 110 W for 30 seconds to 5% Vibrate for minutes to disperse the inorganic filler. About 3 mL of the dispersion liquid is injected into the measuring cell and measurement is performed at 25 ° C. As a measuring device, a laser diffraction type particle size distribution meter (LA920, Horiba, Ltd.) is used to measure the volume-based particle size distribution. The average particle diameter is obtained as a particle diameter (D50%) when the accumulation from the small diameter side is 50% in the volume-based particle size distribution.

  The ratio of the average particle diameter of the first silica particles and the average particle diameter of the second silica particles (average particle diameter of the second silica particles / average particle diameter of the first silica particles) is 7 to 20. It is more preferable, it is more preferable that it is 8-15, and it is still more preferable that it is 9-12.

Whether or not the inorganic filler contains both the first silica particles and the second silica particles is confirmed by, for example, obtaining a volume-based particle size distribution (frequency distribution) of the inorganic filler. Specifically, when there are peaks in the range of 5 nm or more and less than 200 nm and the range of 0.2 μm to 5 μm in the volume-based frequency distribution of the inorganic filler, the inorganic filler is the first silica particles and It can be said to include both second silica particles. The confirmation method is not limited to the above method.
Further, the method for obtaining the proportion of the first or second silica particles in the inorganic filler is not particularly limited. For example, the volume-based particle size distribution (frequency distribution) of the inorganic filler is obtained, and both are separated by a valley between the peak corresponding to the first silica particle and the peak corresponding to the second silica particle, and each of the separated ranges The ratio of the first or second silica particles can be obtained by dividing the volume of the particles contained in 1 by the total volume of the inorganic filler. When the composition of the liquid resin composition is clear, the proportion of the first or second silica particles in the inorganic filler can be determined from the composition of the liquid resin composition. The calculation method is not limited to the above method.

-Curing accelerator-
The liquid resin composition of the present disclosure may contain a curing accelerator. The type of curing accelerator is not particularly limited, and known curing accelerators can be used.
Specifically, 1,8-diaza-bicyclo [5.4.0] undecene-7,1,5-diaza-bicyclo [4.3.0] nonene, 5,6-dibutylamino-1,8- Cycloamidine compounds such as diaza-bicyclo [5.4.0] undecene-7; cycloamidine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethyl Quinone compounds such as benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone and phenyl-1,4-benzoquinone, diazo A compound having an intramolecular polarization formed by adding a compound having a π bond such as phenylmethane or phenol resin; benzyldimethylamine, triethanolamine, Tertiary amine compounds such as methylaminoethanol and tris (dimethylaminomethyl) phenol; derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; imidazole compounds An organic phosphine compound such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine; an organic phosphine compound containing maleic anhydride, the above quinone compound, diazophenylmethane, Phosphorus compounds having intramolecular polarization formed by adding a compound having a π bond such as phenol resin; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetra Tetraphenylboron salts such as phenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate; derivatives of tetraphenylboron salts; triphenylphosphonium-triphenylborane, N-methylmorpholine tetraphenylphosphonium -Addition products of a phosphine compound such as tetraphenylborate and a tetraphenylboron salt, and the like. The curing accelerator may be used alone or in combination of two or more.

  The content of the curing accelerator is preferably 0.1% by mass to 8% by mass with respect to the total amount of the epoxy resin and the curing agent.

-Ion trap agent-
The liquid resin composition of the present disclosure may contain an ion trap agent.
The ion trap agent that can be used in the present disclosure is not particularly limited as long as it is an ion trap agent that is generally used in the encapsulating material used for manufacturing semiconductor devices. Examples of the ion trap agent include compounds represented by the following general formula (VI-1) or the following general formula (VI-2).

_{Mg 1-a Al a (OH} ) 2 (CO 3) a / 2 · uH 2 O (VI-1)
(In the general formula (VI-1), a is 0 <a ≦ 0.5, and u is a positive number.)
_{BiO b (OH) c (NO} 3) d (VI-2)
(In the general formula (VI-2), b is 0.9 ≦ b ≦ 1.1, c is 0.6 ≦ c ≦ 0.8, and d is 0.2 ≦ d ≦ 0.4.)

  The ion trap agent is commercially available. As the compound represented by the general formula (VI-1), for example, “DHT-4A” (Kyowa Chemical Industry Co., Ltd., trade name) is available as a commercial product. In addition, as the compound represented by the general formula (VI-2), for example, “IXE500” (Toagosei Co., Ltd., trade name) is commercially available.

Examples of ion trap agents other than the above include hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like.
The ion trap agents may be used alone or in combination of two or more.

  When the liquid resin composition contains an ion trap agent, the content of the ion trap agent is preferably 1 part by mass or more based on 100 parts by mass of the epoxy resin from the viewpoint of realizing sufficient moisture resistance reliability. . From the viewpoint of sufficiently exerting the effects of other components, the content of the ion trap agent is preferably 15 parts by mass or less, and 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Is more preferable and 2 to 5 parts by mass is further preferable.

  The average particle size of the ion trap agent is preferably 0.1 μm to 3.0 μm, and the maximum particle size is preferably 10 μm or less. The average particle size of the ion trap agent can be measured in the same manner as in the case of the inorganic filler.

-Antioxidant-
The liquid resin composition of the present disclosure may include an antioxidant. As the antioxidant, a conventionally known one can be used.
Examples of the phenol compound-based antioxidant include 2,6-di-t-butyl-4-methylphenol and n-octadecyl-3- (3,5) as compounds having at least one alkyl group in the ortho position of the phenol nucleus. -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 3,9-bis [2- [3- (3-t-butyl) -4-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 4,4'-butylidenebis- (6- t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), tetrakis [methylene-3- (3,5-di-t-butyl-4). Hydroxyphenyl) propionate] methane, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis [3- (3 , 5-Di-t-butyl-4-hydroxyphenyl) propionamide], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2, 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 4,6-bis (dodecylthiomethyl) -o-cresol, bis [3,5-di-t-butyl- 4-Hydroxybenzyl (ethoxy) phosphinate] calcium, 2,4-bis (octylthiomethyl) -6-methylphenol, 1,6-hexanediol-bis [3- 3,5-di-t-butyl-4-hydroxyphenyl) propionate], 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10- Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4- Methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2,2'-methylenebis- (4- Ethyl-6-t-butylphenol), 2,6-di-t-butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, tri Ethylene glycol [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tris (3,5-di-t-butyl-4hydroxybenzyl) isocyanurate, diethyl [[3,5-bis ( 1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 2,5,7,8-tetramethyl-2- (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6-ol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like can be mentioned.
Organic sulfur compound-based antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityl. Tetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, 4,4'-thiobis (6-t-butyl-3-methylphenol), 2, 2-Thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis (dodecylthiomethyl) -o-cresol, 2,4-bis (octyl Thiomethyl) -6-methylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino ) -1,3,5-triazine and the like.
As the amine compound-based antioxidant, N, N'-diallyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, 2,4-bis- (n- Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like.
Among the amine compound-based antioxidants, as dicyclohexylamine, trade name D-CHA-T manufactured by Shin Nippon Rika Co., Ltd. is available as a commercial product, and as its derivative, dicyclohexylamine ammonium, N, N. -Di (3-methyl-cyclohexyl) amine, N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromo-cyclohexyl) amine and the like can be mentioned.
Examples of phosphorus compound-based antioxidants include trisnonylphenyl phosphite, triphenyl phosphite, bis [3,5-di-t-butyl-4-hydroxybenzyl (ethoxy) phosphinate] calcium, tris (2,4-diphenol). -T-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphepin- 6-yl] oxy] -N, N-bis [2-{[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphos Fepin-6-yl] oxy} -ethyl] ethanamine, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t- Butyldibenz [d, f] [1 3,2] dioxaphosphepin, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, and the like.
The antioxidants may be used alone or in combination of two or more. As a specific example of the antioxidant, there is a compound containing at least one of a phosphorus atom, a sulfur atom and an amine in the same molecule in addition to the phenolic hydroxyl group, but these compounds may be mentioned as duplicates. is there.

  The content of the antioxidant is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, based on the whole epoxy resin.

-Organic solvent-
An organic solvent may be added to the liquid resin composition of the present disclosure as needed to reduce the viscosity. In particular, when using a solid epoxy resin and a curing agent, it is preferable to add an organic solvent in order to obtain a liquid resin composition.
The organic solvent is not particularly limited, methyl alcohol, ethyl alcohol, propyl alcohol, alcohol solvents such as butyl alcohol, acetone, ketone solvents such as methyl ethyl ketone, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, Propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate and other glycol ether solvents, γ-butyrolactone, δ-valerolactone, ε-caprolactone and other lactone solvents, dimethylacetamide, dimethyl Examples include amide solvents such as formamide, aromatic solvents such as toluene and xylene, and one type used alone. Also, it may be used in combination of two or more. Among these, an organic solvent having a boiling point of 170 ° C. or higher is preferable from the viewpoint of avoiding bubble formation due to rapid volatilization when curing the liquid resin composition.

The content of volatile matter including an organic solvent is not particularly limited as long as it does not form bubbles when the liquid resin composition is cured, and may be 5% by mass or less with respect to the entire liquid resin composition. It is preferably 1 mass% or less, more preferably 0.1 mass% or less.
In the present disclosure, the volatile matter of the liquid resin composition is calculated based on the weight difference before and after heating the liquid resin composition at 180 ° C. for 30 minutes.

-Release agent-
The liquid resin composition of the present disclosure may contain a release agent. The type of release agent is not particularly limited, and known release agents can be used. Specific examples include higher fatty acids, carnauba wax, and polyethylene wax. The release agent may be used alone or in combination of two or more.
When the liquid resin composition contains a releasing agent, the content of the releasing agent is preferably 10% by mass or less based on the total amount of the epoxy resin and the curing agent, from the viewpoint of exerting the effect. Is preferably 0.5% by mass or more.

-Colorant-
The liquid resin composition of the present disclosure may contain a colorant (for example, carbon black). The colorants may be used alone or in combination of two or more.

When conductive particles such as carbon black are used as the colorant, the conductive particles preferably have a content of particles having a particle diameter of 10 μm or more of 1% by mass or less.
When the liquid resin composition contains conductive particles, the content of the conductive particles is preferably 3% by mass or less based on the total amount of the epoxy resin and the curing agent, and 0.01% by mass to 1% by mass. % Is more preferable.

-Rubber particles-
The liquid resin composition may contain rubber particles from the viewpoint of reducing the thermal expansion of the cured product. The rubber particles may be used alone or in combination of two or more.
Examples of suitable rubber particles include rubber particles such as styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR) and acrylic rubber (AR). Among them, from the viewpoint of heat resistance and moisture resistance, rubber particles containing acrylic rubber are preferable, and core-shell type acrylic rubber particles are more preferable.

Moreover, silicone rubber particles are mentioned as another example of a suitable rubber particle.
As the silicone rubber particles, silicone rubber particles obtained by crosslinking a linear polyorganosiloxane such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane; those whose surface is coated with silicone resin, emulsion polymerization Core-shell polymer particles including a core of solid silicone particles obtained by the above and a shell of an organic polymer such as an acrylic resin. The shape of these silicone rubber particles may be amorphous or spherical, and it is preferable to use spherical silicone rubber particles in order to keep the viscosity of the liquid resin composition low.
The silicone rubber particles are commercially available from Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., etc.

When the liquid resin composition contains rubber particles, the average particle diameter of the rubber particles is preferably fine in order to uniformly modify the liquid resin composition. The average particle diameter of the rubber particles is preferably in the range of 0.05 μm to 10 μm, more preferably 0.1 μm to 5 μm. When the average particle diameter of the rubber particles is 0.05 μm or more, the dispersibility in the liquid resin composition tends to be further improved. If the volume average particle diameter of the rubber particles is 10 μm or less, the effect of improving the stress reduction tends to be further improved, and the permeability and fluidity into the fine voids as the liquid resin composition are improved, resulting in voids and unfilling. Tend to be difficult to invite.
The average particle diameter of the rubber particles is measured using the same method as the inorganic filler.

<Method for producing liquid resin composition>
The liquid resin composition is, for example, first silica particles having an average particle size of 5 nm or more and less than 200 nm, which are surface-treated with (A) an epoxy resin, (B) a curing agent, and (C) a silane coupling agent having an epoxy group. , And (D) the second silica particles having an average particle diameter of 0.2 μm to 5 μm, and other components used as necessary, collectively or separately, with stirring if necessary, and melting. It can be obtained by mixing, dispersing or the like. A device for mixing, stirring, dispersing, etc. of these components is not particularly limited, and a Leika machine equipped with a stirring device, a heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. Can be mentioned. A liquid resin composition can be obtained by mixing the above components using these devices, kneading, and defoaming as necessary.
As the first silica particles, a mixture in which the first silica particles are mixed in advance with an epoxy resin may be used for the purpose of improving the dispersibility of the first silica particles. In this case, the content of the first silica particles in the mixture is preferably 20% by mass to 70% by mass.

  The viscosity of the liquid resin composition is not particularly limited. Among them, from the viewpoint of high fluidity, it is preferably 0.1 Pa · s to 50.0 Pa · s at 25 ° C, more preferably 1.0 Pa · s to 50.0 Pa · s, and 10.0 Pa · s. It is more preferably s to 50.0 Pa · s. The viscosity of the liquid resin composition is measured at 25 ° C. using an E-type viscometer (cone angle 3 °, rotation speed 10 rotations / minute).

  Further, when the liquid resin composition is used for an application such as an underfill material, the ease of filling when filling the liquid resin composition in a narrow gap of several tens μm to several hundreds μm near 100 ° C. to 120 ° C. As an index of, the viscosity at 110 ° C. is preferably 0.20 Pa · s or less, more preferably 0.15 Pa · s or less, and 0.12 Pa.s. It is more preferably s or less. The viscosity of the liquid resin composition at 110 ° C. is measured by a rheometer AR2000 (TA Instruments, aluminum cone 40 mm, shear rate 32.5 / sec).

  Further, the liquid resin composition is a thixotropic index which is a ratio of a viscosity at a rotation speed of 2.5 rotations / minute measured at 25 ° C. using an E-type viscometer and a viscosity at a rotation speed of 10 rotations / minute. [(Viscosity at 2.5 rpm) / (Viscosity at 10 rpm)] is preferably 0.3 to 1.5, and more preferably 0.5 to 1.2. When the thixotropic index is in the above range, the filling property tends to be further improved. The viscosity and the thixotropic index of the liquid resin composition can be set within desired ranges by appropriately selecting the composition of the epoxy resin, the content rate of the inorganic filler, and the like.

  The curing conditions of the liquid resin composition are not particularly limited, and it is preferable to heat at 80 ° C to 165 ° C for 1 minute to 150 minutes.

<Electronic component device>
The electronic component device of the present disclosure includes a substrate having a circuit layer, an electronic component disposed on the substrate and electrically connected to the circuit layer, and a book disposed in a gap between the substrate and the electronic component. And a cured product of the disclosed liquid resin composition. The electronic component device of the present disclosure can be obtained by sealing an electronic component with the liquid resin composition of the present disclosure. Since the electronic component is sealed with the liquid resin composition, the electronic component device of the present disclosure has excellent reliability.

Electronic component devices include lead frames, wired tape carriers, rigid wiring boards, flexible wiring boards, substrates having circuit layers such as glass and silicon wafers, active elements such as semiconductor chips, transistors, diodes, thyristors, and capacitors. An electronic component device obtained by mounting an electronic component such as a resistor, a resistor array, a coil, and a passive element such as a switch, and sealing a necessary portion with the liquid resin composition of the present disclosure can be given.
In particular, a semiconductor device in which a semiconductor element is flip-chip bonded by bump connection to a wiring formed on a rigid wiring board, a flexible wiring board or glass is mentioned as one of the objects to which the liquid resin composition of the present disclosure can be applied. . Specific examples include electronic component devices such as flip chip BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film).

  The liquid resin composition of the present disclosure is suitable as an underfill material for flip chips, which has excellent reliability. The field of flip chip to which the liquid resin composition of the present disclosure is particularly preferably applied is not only the case where the bump material connecting the wiring board and the semiconductor element is a conventional lead-containing solder, but also a Sn-Ag-Cu system. A flip-chip semiconductor component using lead-free solder such as the above can also be mentioned. The liquid resin composition of the present disclosure tends to maintain good reliability even for a flip chip in which bump connection is performed using a lead-free solder, which is physically more brittle than conventional lead solder. Also, when the chip scale package such as a wafer level CSP (Chip Size Package) is mounted on a substrate, the liquid resin composition of the present disclosure may be applied to improve reliability.

<Method of manufacturing electronic component device>
A method of manufacturing an electronic component device of the present disclosure, a substrate having a circuit layer, and an electronic component disposed on the substrate and electrically connected to the circuit layer, using the liquid resin composition of the present disclosure There is a step of sealing.
There is no particular limitation on the step of sealing the electronic component with the substrate having the circuit layer using the liquid resin composition of the present disclosure. For example, after connecting an electronic component and a substrate having a circuit layer, a liquid resin composition is applied to the gap between the electronic component and the substrate by utilizing a capillary phenomenon, and then a curing reaction of the liquid resin composition is performed. Method, and when the liquid resin composition of the present disclosure is applied to at least one surface of the substrate and the electronic component having the circuit layer, and when the electronic component is connected to the substrate by thermocompression bonding, An example is a pre-coating method in which the connection and the curing reaction of the liquid resin composition are performed at once.
Examples of the method of applying the liquid resin composition include a casting method, a dispensing method, a printing method and the like.

  Hereinafter, the present invention will be described based on Examples, but the present invention is not limited to the following Examples. In the following examples, parts and% indicate parts by mass and% by mass, unless otherwise specified.

(Examples 1-5 and Comparative Examples 1-9)
Each of the components was blended so as to have the composition shown in Table 1 and Table 2, kneaded with a three-roll and vacuum lysing machine, and dispersed to obtain each of Examples 1 to 5 and Comparative Examples 1 to 9. A liquid resin composition was prepared. In addition, the compounding unit in a table is a mass part, and "-" represents "no compounding".

The materials used for producing the liquid resin composition and their abbreviations are shown below.
(A) Epoxy resin / epoxy resin 1: bisphenol F type epoxy resin (epoxy equivalent: 160 g / eq, viscosity at 25 ° C .: 1 Pa · s to 2 Pa · s)
Epoxy resin 2: aminophenol type trifunctional epoxy resin (epoxy equivalent: 95 g / eq, viscosity at 25 ° C .: 0.5 Pa · s to 1.0 Pa · s)
Epoxy resin 3: polypropylene glycol type bifunctional epoxy resin (epoxy equivalent: 315 g / eq, viscosity at 25 ° C .: 0.04 Pa · s to 0.06 Pa · s)

(B) Hardener / Hardener 1: Diethyltoluenediamine (amine equivalent: 45 g / eq)
-Curing agent 2: 4,4'-methylenebis (2-ethylaniline) (amine equivalent: 63 g / eq)

(C) First silica particles / nanosilica particles 1: average particle size 50 nm, treated with phenylsilane, nanosilica particles 2: average particle size 50 nm, treated with 3-glycidoxypropyltrimethoxysilane, nanosilica particles 3: average particles 50 nm in diameter, treated with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, nanosilica particles 4: average particle diameter 20 nm, treated with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, nanosilica particles 5: Treatment with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane having an average particle diameter of 10 nm (D) Second silica particles / microsilica particles: average particle diameter 0.5 μm

-Curing accelerator: triphenylphosphine-Colorant: carbon black (containing 90% dispersant, 10% carbon black as solid content), average particle diameter 24 nm
・ Ion trap agent: Bismuth-based ion trap agent ・ Antioxidant: Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane

(1) Flowability: viscosity and thixotropic index The viscosity (viscosity (25 ° C.), Pa · s) of the liquid resin composition at 25 ° C. was measured by an E-type viscometer (cone angle 3 °, rotation speed 10 rotations / minute). Was measured using. Further, the thixotropic index at 25 ° C. is the ratio of the viscosity at a rotation speed of 2.5 rpm to the viscosity at a rotation speed of 10 rpm [(viscosity at 2.5 rpm) / (10 rpm / Viscosity in minutes)].
The viscosity at 110 ° C. (viscosity (110 ° C.), Pa · s) was measured using a rheometer AR2000 (aluminum cone 40 mm, shear rate 32.5 / sec).
The obtained results are shown in Table 1 or Table 2.

(Filling time)
A test piece was prepared by fixing a glass plate (20 mm × 30 mm × 1 mm thickness) instead of the semiconductor element with a gap of 10 μm provided on the slide glass. This test piece is placed on a hot plate heated to 110 ° C., the liquid resin composition is applied to the side surface (one side) of the glass plate, and the liquid resin composition permeates between the slide glass and the glass plate to the opposite side surface. The time to reach it was measured.
The obtained results are shown in Table 1 or Table 2.
The “impossible” in the filling time of Comparative Example 9 means that the filling of the liquid resin composition did not reach the opposite side surfaces.

In Tables 1 and 2, "silica content" means the proportion of the total of (C) first silica particles and (D) second silica particles, and "silica ratio" means (C) A mass-based ratio of (1) silica particles and (D) second silica particles ((D) second silica particles / (C) first silica particles) is meant, and the "particle size ratio" is (C ) It means the ratio of the average particle diameter of the first silica particles and the average particle diameter of the (D) second silica particles ((D) second silica particles / (C) first silica particles).
As is clear from Tables 1 and 2, the filling time of the liquid resin compositions of the examples is shorter than the filling time of the liquid resin compositions of the comparative examples. Therefore, it can be seen that the liquid resin composition of the present disclosure has excellent filling properties.

Claims (9)

(A) Epoxy resin, (B) curing agent, (C) first silica particles having an average particle size of 5 nm or more and less than 200 nm, which are surface-treated with a silane coupling agent having an epoxy group, and (D) average particles Including second silica particles having a diameter of 0.2 μm to 5 μm,
The ratio of the total of the (C) first silica particles and the (D) second silica particles is 40% by mass to 80% by mass,
The mass-based ratio of the (C) first silica particles to the (D) second silica particles ((D) second silica particles / (C) first silica particles) is 2 to 10. Liquid resin composition.   The liquid resin composition according to claim 1, wherein the viscosity of the (A) epoxy resin at 25 ° C. is 1000 Pa · s or less.   The liquid resin composition according to claim 1, wherein the curing agent (B) contains an amine curing agent.   The liquid resin composition according to any one of claims 1 to 3, which contains an ion trap agent.   The liquid resin composition according to any one of claims 1 to 4, which contains a curing accelerator.   The liquid resin composition according to any one of claims 1 to 5, which contains an antioxidant.   The liquid resin composition according to any one of claims 1 to 6, which has a volatile content of 5% by mass or less. A substrate having a circuit layer,
An electronic component disposed on the substrate and electrically connected to the circuit layer,
A cured product of the liquid resin composition according to claim 1, which is disposed in a gap between the substrate and the electronic component.
An electronic component device including.   The liquid resin composition according to claim 1, wherein a substrate having a circuit layer and an electronic component arranged on the substrate and electrically connected to the circuit layer are used. A method for manufacturing an electronic component device, which comprises a step of sealing by means of a method.