JP7404620B2 - Liquid resin composition, electronic component device, and manufacturing method thereof - Google Patents

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 for electronic component devices such as transistors and ICs (Integrated Circuits), resin encapsulation has been the mainstream from the viewpoint of productivity and cost, and various types of resin compositions have been applied. . Among these, epoxy resins are widely used because they have well-balanced properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products. BACKGROUND ART Liquid resin compositions for electronic components are widely used as encapsulants in semiconductor devices mounted with bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package). In addition, in a semiconductor device (flip chip) in which a semiconductor element is directly bump-connected to a wiring board made of ceramic, glass/epoxy resin, glass/imide resin, polyimide film, etc., the bump-connected semiconductor element and the wiring board are Liquid resin compositions for electronic components are used as underfill materials to fill gaps in gaps. These liquid resin compositions for electronic components play an important role in protecting electronic components from temperature, humidity, external mechanical forces, and the like.

For example, to provide an epoxy resin composition for sealing with excellent moisture-resistant adhesive strength and low stress, and an electronic component device with high reliability (humidity resistance and thermal shock resistance) equipped with an element sealed thereby. , (A) a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) rubber particles, and (D) an encapsulating epoxy resin composition containing an inorganic filler, and this encapsulating epoxy resin composition. An electronic component device including an element sealed with an epoxy resin composition has been disclosed (see, for example, Patent Document 1).

Japanese Patent Application Publication No. 2001-270976

However, advances in semiconductors have been remarkable, 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, and as a result, the gap has become narrower. As semiconductors become more highly integrated, chip sizes also increase, and underfill materials are required to have the ability to uniformly fill large-area voids with narrow gaps.

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

Specific means for achieving the above object are as follows.
<1> (A) an epoxy resin, (B) a curing agent, (C) first silica particles having an average particle diameter of 5 nm or more and less than 200 nm, surface-treated with a silane coupling agent having a glycidyl group, and (D ) second silica particles having an average particle diameter of 0.2 μm to 5 μm,
The total proportion of the first silica particles (C) and the second silica particles (D) is 40% by mass to 80% by mass,
The mass-based ratio of the (C) first silica particles and the (D) second silica particles ((D) second silica particles/(C) first silica particles) is 5 to 600. Liquid resin composition.
<2> The liquid resin composition according to <1>, wherein the epoxy resin (A) has a viscosity of 1000 Pa·s or less at 25°C.
<3> The liquid resin composition according to <1> or <2>, wherein the curing agent (B) includes an amine curing agent.
<4> The liquid resin composition according to any one of <1> to <3>, which contains an ion trapping 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>, wherein the content of volatile matter is 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>, disposed in a gap between the substrate and the electronic component;
An electronic component device comprising:
<9> 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 according to any one of <1> to <7>. A method for manufacturing an electronic component device, which includes a step of sealing using a material.

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

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, the constituent elements (including elemental steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and they do not limit the present invention.
In this disclosure, the term "step" includes not only a step that is independent from other steps, but also a step that cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved. .
In the present disclosure, numerical ranges indicated using "~" include the numerical values written before and after "~" as minimum and maximum values, respectively.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. . Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
In the present disclosure, each component may contain multiple types of corresponding substances. If there are multiple types of substances corresponding to each component 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, each component may include a plurality of types of particles. When a plurality of types 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 types of particles present in the composition, unless otherwise specified.
In this disclosure, the term "layer" includes not only the case where the layer is formed in the entire area when observing the area where the layer exists, but also the case where the layer is formed only in a part of the area. included.

<Liquid resin composition>
The liquid resin composition of the present disclosure includes a first silica resin having an average particle diameter 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 a glycidyl group. particles, and (D) second silica particles having an average particle diameter of 0.2 μm to 5 μm, and the total proportion 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) is 5 to 600.
The liquid resin composition of the present disclosure has excellent filling properties. Although the reason is not clear, it is inferred as follows.
When 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 a glycidyl group, the wettability between the silica particles and the epoxy resin is improved. Further, by using together 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 improves, and as a result, the viscosity of the liquid resin composition decreases, so it is presumed that the liquid resin composition of the present disclosure has excellent filling properties.

Each component constituting the liquid resin composition will be explained below. The liquid resin composition of the present disclosure includes a first silica resin having an average particle diameter 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 a glycidyl 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 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. Preferably, the epoxy resin is a liquid epoxy resin. In the present disclosure, a solid epoxy resin can also be used in combination with a liquid epoxy resin.

Note that the liquid epoxy resin means an epoxy resin that is liquid at room temperature (25° C.). Specifically, it means that the viscosity measured with an E-type viscometer at 25° C. is 1000 Pa·s or less. Specifically, the above viscosity was 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 sample rotation speed with reference to the following. The value is set according to the expected viscosity, and the value is measured one minute after the start of measurement.
(1) When the expected viscosity is 100 Pa・s to 1000 Pa・s: rotation speed 0.5 rotations/min (2) When the assumed viscosity is less than 100 Pa・s: rotation speed 5 rotations/minute Epoxy resin means an epoxy resin that is solid at room temperature (25° C.).

The type of epoxy resin is not particularly limited. Epoxy resins include naphthalene type epoxy resins; diglycidyl ether type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; and phenols and aldehydes, typified by orthocresol novolac type epoxy resins. Glycidyl ester type epoxy resin obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; Amine compounds such as diaminodiphenylmethane, isocyanuric acid, and aminophenol. Examples include glycidylamine-type epoxy resins obtained by the reaction of and 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 even more preferable.
The epoxy equivalent of an epoxy resin is measured by dissolving a weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and a solution of tetraethylammonium bromide in acetic acid, and then performing potentiometric titration with a standard solution of perchloric acid and acetic acid. An indicator may be used for this titration.

As the epoxy resin, commercially available products may be used. 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., and Nippon Steel & Sumikin Chemical Co., Ltd. Bisphenol A type epoxy resin (product name: YD-128) manufactured by DIC Corporation, naphthalene type epoxy resin manufactured by DIC Corporation (product name: HP-4032D), product name "Epogose PT (general grade)" (Yokkaichi Gosei Co., Ltd., polytetramethylene glycol) diglycidyl ether, number average molecular weight 700 to 800), etc. The epoxy resin is not limited to these specific examples. Epoxy resins may be used singly or in combination of two or more.
The content of the epoxy resin is not particularly limited, and for example, it is preferably 5% to 30% by mass, and preferably 7% to 28% by mass based on the solid content of the liquid resin composition. The amount is more preferably 10% by mass to 25% by mass.

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

Examples of the amine curing agent include chain aliphatic amines, cyclic aliphatic amines, aliphatic amines, aromatic amines, etc. From the viewpoint of heat resistance and electrical properties, aromatic amines are preferred; It is more preferable that the amine is an aromatic amine in which an amino group is directly bonded to and one or two aromatic rings are contained in one molecule.
Specifically, the amine curing agent includes 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 with one aromatic ring; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone , 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, Aromatic amine curing agents with two aromatic rings such as 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane; hydrolyzed condensates of aromatic amine curing agents; polytetramethylene oxide di- Aromatic amine curing agents having a polyether structure such as p-aminobenzoic acid ester and polytetramethylene oxide dipraminobenzoate; condensates of aromatic diamines and epichlorohydrin; reaction products of aromatic diamines and styrene Examples include.

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

Examples of acid anhydride curing agents include phthalic anhydride, maleic anhydride, methylhimic anhydride, himic acid anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydro Phthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, Examples include various cyclic acid anhydrides such as hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride having multiple alkyl groups, and dodecenylsuccinic anhydride obtained by Diels-Alder reaction from maleic anhydride and a diene compound. .

The phenolic curing agent is selected from the group consisting of phenolic compounds (e.g. phenol, cresol, xylenol, resorcinol, catechol, bisphenol A and bisphenol F) and naphthol compounds (e.g. α-naphthol, β-naphthol and dihydroxynaphthalene). and an aldehyde compound (for example, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde) under an acidic catalyst; a novolac resin obtained by condensing or co-condensing at least one of the following: phenol/aralkyl resin; biphenyl/aralkyl resins; and naphthol aralkyl resins.
One type of curing agent may be used alone, or two or more types may be used in combination.

The number of equivalents of the functional group of the curing agent (for example, an amino group in the case of an amine curing agent, a phenolic hydroxyl group in the case of a phenolic curing agent, an acid anhydride group in the case of an acid anhydride curing agent) and 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. It is more preferable to set it in the range of 0.8 to 1.2.

-Inorganic filler-
The liquid resin composition of the present disclosure includes, as an inorganic filler, (C) first silica particles having an average particle diameter of 5 nm or more and less than 200 nm, which are surface-treated with a silane coupling agent having a glycidyl group, and (D) Contains second silica particles having an average particle size of 0.2 μm to 5 μm.
Examples of the silica particles include colloidal silica, hydrophobic silica, spherical silica, etc. From the viewpoint of fluidity of the liquid resin composition, heat resistance of the cured product of the liquid resin composition, etc., amorphous spherical silica is used. It is preferable.
As the amorphous spherical silica, amorphous spherical silica produced by a sol-gel method is also preferred from the viewpoint of particle size controllability and purity. Note that as the silica, a composition containing silica obtained by the manufacturing method described in JP-A No. 2007-197655 may be used.

The total proportion of the first silica particles and the second silica particles is 40% by mass to 80% by mass, preferably 45% to 75% by mass, and 50% to 75% by mass. It is more preferable.
The mass-based ratio of the first silica particles and the second silica particles (second silica particles/first silica particles) is from 5 to 600, preferably from 5 to 300, and from 5 to 100. The number is more preferably 5 to 75, and even more preferably 5 to 75.
The liquid resin composition of the present disclosure may contain 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. Furthermore, examples of inorganic fillers having flame retardant effects include aluminum hydroxide, zinc borate, and the like.
The content of other inorganic fillers in the inorganic filler is preferably 10% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

When the total content of silica particles in the liquid resin composition is the same, the first silica particles are used together with the second silica particles compared to the case where only the second silica particles are used as the inorganic filler. By using them together, the viscosity of the liquid resin composition tends to be lowered. Therefore, there is a tendency that the total content of silica particles can be increased without causing an increase in the viscosity of the liquid resin composition. As the total content of silica particles increases, the coefficient of thermal expansion of the cured product of the liquid resin composition decreases, and as a result, the reliability of electronic component devices sealed with the liquid resin composition tends to improve. be.

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, 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 less likely to increase, and fluidity tends to be less likely to deteriorate. When the average particle diameter of the first silica particles is less than 200 nm, the viscosity of the liquid resin composition tends to be lowered.

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

The first silica particles are surface-treated with a silane coupling agent having a glycidyl group. Examples of the silane coupling agent having a glycidyl group include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxy Examples include silane. These compounds are commercially available from Shin-Etsu Chemical Co., Ltd. and the like. Note that the silane coupling agent having a glycidyl group does not include a silane coupling agent having an alicyclic epoxy group such as a 3,4-epoxycyclohexyl group.

The method for surface treating silica particles with a silane coupling agent having a glycidyl group is not particularly limited, and any commonly used surface treatment method can be appropriately selected. For example, a method in which a solution containing a silane coupling agent having a glycidyl group is added to a slurry containing silica particles, the mixture is stirred, and the surface-treated silica particles are separated by filtration or the like and dried; Examples include a method in which a coupling agent is sprayed onto silica particles and dried.

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

As the first silica particles, commercially available products may be used. Specific examples of commercial products of the first silica particles include inorganic fillers manufactured by Admatex Co., Ltd. (product names: YA010C, YA050C, etc.), inorganic fillers manufactured by Sakai Chemical Industry Co., Ltd. (product name: Sciqas 0.05 μm), 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 types.

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 30% by mass or less. The proportion of the first silica particles in the inorganic filler is preferably 0.3% to 30% by mass, more preferably 0.5% to 25% by mass, and 1% to 20% by mass. More preferably, it is expressed in mass %. If the proportion of the first silica particles in the inorganic filler is within the above range, a liquid resin composition that can exhibit an effect of reducing bleeding and has excellent fluidity will tend to be obtained.

The second silica particles impart heat cycle resistance, moisture resistance, insulation properties, etc. 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 2 μm, and 0.4 μm to 1.8 μm. It is even more preferable that there be.
From the viewpoint of fluidity, the specific surface area of the second silica particles is preferably 1 m ² /g to 30 m 2 /g, more preferably 2 m ² /g to 20 ^{m 2 /} g.

The proportion of the second silica particles in the inorganic filler is preferably 70% 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 70% by mass to 99.7% by mass, and even more preferably 75% 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 alkyl groups such as methyl group and ethyl group.

As the second silica particles, commercially available products may be used. Specific examples of commercially available second silica particles include spherical silica manufactured by Admatex Co., Ltd. (product name: SO-E2), spherical silica manufactured by Admatex Co., Ltd. (product name: SE2200), etc. Silica particles are not limited to these specific examples.
The second silica particles may be used alone or in combination of two or more types.

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 the evaluation device, AUTOSORB-1 (trade name) manufactured by QUANTACHROME can be used. Since moisture adsorbed on the sample surface and structure is thought to affect the gas adsorption ability, when measuring the BET specific surface area, it is preferable to first perform pretreatment to remove moisture by heating. .
In the pretreatment, the measurement cell containing 0.05 g of the measurement sample was depressurized to 10 Pa or less using a vacuum pump, heated to 110°C, held for more than 3 hours, and then heated to room temperature (while maintaining the depressurized state). Cool naturally to 25°C. After performing this pretreatment, the evaluation temperature is set to 77 K, and the evaluation pressure range is measured as relative pressure (equilibrium pressure with respect to saturated vapor pressure) less than 1.

The average particle diameter of the inorganic filler can be measured by the following method.
Add the inorganic filler to be measured to a solvent (pure water) in a range of 1% to 5% by mass together with 1% to 8% by mass of a surfactant, and wash in a 110W ultrasonic cleaner for 30 seconds to 5%. Vibrate for a minute to disperse the inorganic filler. About 3 mL of the dispersion liquid is injected into a measurement cell and measured at 25°C. The measuring device measures the volume-based particle size distribution using a laser diffraction particle size distribution meter (Horiba, Ltd., LA920). The average particle diameter is determined as the 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 to 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 40. It is preferably from 8 to 35, even more preferably from 9 to 32.

Whether or not the inorganic filler contains both the first silica particles and the second silica particles is confirmed, for example, by determining the volume-based particle size distribution (frequency distribution) of the inorganic filler. Specifically, in the volume-based frequency distribution of the inorganic filler, if peaks exist in the range of 5 nm or more and less than 200 nm and in the range of 0.2 μm to 5 μm, the inorganic filler is the first silica particle and the second silica particle. It can be said that it contains both silica particles. Note that the confirmation method is not limited to the above method.
Furthermore, the method for determining 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 determined, the peak corresponding to the first silica particle and the peak corresponding to the second silica particle are divided into valleys, and each of the divided ranges is The proportion of the first or second silica particles can be determined by dividing the volume of the particles contained in the inorganic filler by the total volume of the inorganic filler. When the composition of the liquid resin composition is known, the proportion of the first or second silica particles in the inorganic filler can be determined from the composition of the liquid resin composition. Note that 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 any known curing accelerator 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- Cyclamidine compounds such as diaza-bicyclo[5.4.0]undecene-7; maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethyl in the cycloamidine compound Quinone compounds such as benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazo Compounds with intramolecular polarization obtained by adding compounds with π bonds such as phenylmethane and phenol resins; Tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; Derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4- Organic phosphine compounds such as methylphenylphosphine, diphenylphosphine, and phenylphosphine; intramolecular polarization obtained by adding compounds with π bonds such as maleic anhydride, the above quinone compounds, diazophenylmethane, and phenol resins to organic phosphine compounds; Phosphorus compounds having; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate; derivatives of tetraphenylboron salts ; Examples include adducts of phosphine compounds such as triphenylphosphonium-triphenylborane, N-methylmorpholinetetraphenylphosphonium-tetraphenylborate, and tetraphenylboron salts. One type of curing accelerator may be used alone or two or more types may be used in combination.

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

-Ion trapping agent-
The liquid resin composition of the present disclosure may contain an ion trapping agent.
The ion trapping agent that can be used in the present disclosure is not particularly limited as long as it is a commonly used ion trapping agent in sealing materials used for manufacturing semiconductor devices. Examples of the ion trapping 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 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 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.)

Ion trapping agents are 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. Further, as a compound represented by the general formula (VI-2), for example, "IXE500" (Toagosei Co., Ltd., trade name) is available as a commercial product.

In addition, examples of ion trapping agents other than those mentioned above include hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like.
One type of ion trapping agent may be used alone, or two or more types may be used in combination.

When the liquid resin composition contains an ion trapping agent, the content of the ion trapping agent is preferably 1 part by mass or more per 100 parts by mass of the epoxy resin from the viewpoint of achieving sufficient moisture resistance reliability. . From the viewpoint of fully exhibiting the effects of other components, the content of the ion trapping agent is preferably 15 parts by mass or less, and 1 part by mass to 10 parts by mass, based on 100 parts by mass of the epoxy resin. is more preferable, and even more preferably 2 parts by weight to 5 parts by weight.

Further, the average particle size of the ion trapping agent is preferably 0.1 μm to 3.0 μm, and the maximum particle size is preferably 10 μm or less. The average particle diameter of the ion trapping 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 also contain an antioxidant. As the antioxidant, conventionally known antioxidants can be used.
Examples of phenolic compound antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3-(3,5 -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-hydroxy) phenyl)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-methylphenylacrylate, 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, triethylene glycol-bis[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- Examples include octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine.
Examples of organic sulfur compound antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and 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, etc. .
Examples of amine compound-based antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, and 2,4-bis-(n- Examples include octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine.
Among amine compound-based antioxidants, dicyclohexylamine is commercially available under the trade name D-CHA-T manufactured by Shin Nippon Chemical Co., Ltd., and its derivatives include dicyclohexylamine ammonium nitrite, N,N -di(3-methyl-cyclohexyl)amine, N,N-di(2-methoxy-cyclohexyl)amine, N,N-di(4-bromo-cyclohexyl)amine, and the like.
Examples of phosphorus compound-based antioxidants include trisnonylphenylphosphite, triphenylphosphite, bis[3,5-di-t-butyl-4-hydroxybenzyl(ethoxy)phosphinate]calcium, tris(2,4-di -t-butylphenyl)phosphite, 2-[[2,4,8,10-tetrakis(1,1-dimethylether)dibenzo[d,f][1,3,2]dioxaphosphepine- 6-yl]oxy]-N,N-bis[2-{[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphos phepin-6-yl]oxy}-ethyl]ethanamine, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t- Examples include butyldibenz[d,f][1,3,2]dioxaphosphepine, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, and the like.
One type of antioxidant may be used alone, or two or more types may be used in combination. In addition, as specific examples of antioxidants, there are compounds that contain at least one of a phosphorus atom, a sulfur atom, and an amine in the same molecule in addition to a phenolic hydroxyl group, but these compounds may be listed more than once. be.

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

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

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

-Release agent-
The liquid resin composition of the present disclosure may contain a mold release agent. The type of mold release agent is not particularly limited, and any known mold release agent can be used. Specific examples include higher fatty acids, carnauba wax, and polyethylene wax. One type of mold release agent may be used alone, or two or more types may be used in combination.
When the liquid resin composition contains a mold release agent, the content of the mold release 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 exhibiting its effect. is preferably 0.5% by mass or more.

-Coloring agent-
The liquid resin composition of the present disclosure may contain a colorant (eg, carbon black). One type of colorant may be used alone, or two or more types may be used in combination.

When using conductive particles such as carbon black as a coloring agent, it is preferable that the content of conductive particles having a particle diameter of 10 μm or more is 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 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 thermal expansion of the cured product. One type of rubber particles may be used alone, or two or more types may be used in combination.
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 these, from the viewpoint of heat resistance and moisture resistance, rubber particles containing acrylic rubber are preferred, and core-shell type acrylic rubber particles are more preferred.

Other examples of suitable rubber particles include silicone rubber particles.
Examples of silicone rubber particles include silicone rubber particles crosslinked with linear polyorganosiloxane such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane; silicone rubber particles whose surface is coated with silicone resin, and emulsion polymerization. Examples include core-shell polymer particles comprising a core of solid silicone particles obtained by et al. 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 in order to keep the viscosity of the liquid resin composition low, it is preferable to use spherical silicone rubber particles.
Silicone rubber particles are commercially available from Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., and the like.

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 in the range of 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. When the volume average particle diameter of the rubber particles is 10 μm or less, the stress reduction improvement effect tends to be further improved, and the permeability and fluidity of the liquid resin composition into fine gaps is improved, eliminating voids and unfilled spaces. It tends to be difficult to invite
The average particle diameter of the rubber particles is measured using the same method as for inorganic fillers.

<Method for producing liquid resin composition>
The liquid resin composition includes, for example, first silica particles having an average particle diameter 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 a glycidyl 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, all at once or separately, with stirring and melting while applying heat treatment as necessary. , mixing, dispersion, etc. Devices for mixing, stirring, dispersing, etc. these components are not particularly limited, and include a Raikai 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 and kneading the above components using these devices, and defoaming if necessary.
As the first silica particles, a mixture in which the first silica particles are mixed with an epoxy resin in advance 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, more preferably 1.0 Pa·s to 50.0 Pa·s, and 10.0 Pa·s at 25°C. More preferably, it is from 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 revolutions/min).

In addition, when using the liquid resin composition for applications such as underfill materials, ease of filling when filling the liquid resin composition into a narrow gap of several tens of μm to several hundred μm at around 100°C to 120°C As an index, the viscosity at 110° C. is preferably 0.20 Pa·s or less, more preferably 0.15 Pa·s or less. The viscosity of the liquid resin composition at 110° C. is measured using a rheometer AR2000 (manufactured by TA Instruments, aluminum cone 40 mm, shear rate 32.5/sec).

In addition, the liquid resin composition has a thixotropic index, which is the ratio of the viscosity at a rotational speed of 2.5 rotations/min and the viscosity at a rotational speed of 10 rotations/min, as measured at 25° C. using an E-type viscometer. [(Viscosity at 2.5 revolutions/min)/(Viscosity at 10 revolutions/min)] is preferably from 0.3 to 1.5, more preferably from 0.5 to 1.2. When the thixotropy index is within the above range, the filling properties tend to be further improved. The viscosity and thixotropy index of the liquid resin composition can be set within a desired range by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, and the like.

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

<Electronic component equipment>
An electronic component device of the present disclosure includes a substrate having a circuit layer, an electronic component placed on the substrate and electrically connected to the circuit layer, and a book placed in a gap between the substrate and the electronic component. 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 semiconductor chips, active elements such as transistors, diodes, thyristors, and capacitors on substrates with circuit layers such as lead frames, pre-wired tape carriers, rigid wiring boards, flexible wiring boards, glass, and silicon wafers. Examples include electronic component devices that are obtained by mounting electronic components such as resistors, resistor arrays, coils, passive elements such as switches, and sealing necessary portions with the liquid resin composition of the present disclosure.
In particular, a semiconductor device in which a semiconductor element is flip-chip bonded to a rigid wiring board, a flexible wiring board, or wiring formed on glass by bump connection is 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 with excellent reliability. The field of flip chips to which the liquid resin composition of the present disclosure is particularly suitably applied includes not only cases where the bump material connecting a wiring board and a semiconductor element is a conventional lead-containing solder, but also Sn-Ag-Cu based solder. Examples include flip-chip semiconductor components using lead-free solder such as. The liquid resin composition of the present disclosure tends to maintain good reliability even for flip chips that are bump-connected using lead-free solder, which is physically more fragile than conventional lead solder. Further, by applying the liquid resin composition of the present disclosure even when mounting a chip scale package such as a wafer level CSP (Chip Size Package) on a substrate, reliability tends to be improved.

<Method for manufacturing electronic component devices>
A method for manufacturing an electronic component device of the present disclosure includes 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. It has a sealing step.
There is no particular limitation on the step of sealing a circuit layer-containing substrate and an electronic component using the liquid resin composition of the present disclosure. For example, after connecting an electronic component and a board having a circuit layer, a liquid resin composition is applied to the gap between the electronic component and the board using capillary action, and then a curing reaction of the liquid resin composition is performed. method, and when the liquid resin composition of the present disclosure is first applied to the surface of at least one of a substrate having a circuit layer and an electronic component, and the electronic component is connected to the substrate by thermocompression bonding, the electronic component and the substrate are An example is a pre-coating method in which the connection and the curing reaction of the liquid resin composition are performed at the same time.
Examples of the method for applying the liquid resin composition include a casting method, a dispensing method, and a printing method.

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

(Examples 1 to 4 and Comparative Examples 1 to 8)
Each component was blended to have the composition shown in Tables 1 and 2, kneaded and dispersed using a three-roll machine and a vacuum machine, and then prepared in Examples 1 to 4 and Comparative Examples 1 to 8. A liquid resin composition was produced. In addition, the blending unit in the table is parts by mass, and "-" represents "no blending".

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

(C) First silica particle - Nano silica particle 1: average particle diameter 50 nm, treated with phenylsilane - Nano silica particle 2: average particle diameter 50 nm, treated with 3-glycidoxypropyltrimethoxysilane - Nano silica particle 3: average particle Diameter 20 nm, treatment with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane Nanosilica particles 4: Average particle size 10 nm, treatment with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (D) Second Silica particles/micro silica particles 1: average particle diameter 0.5 μm
・Micro silica particles 2: average particle diameter 1.5 μm

・Curing accelerator: Triphenylphosphine ・Coloring agent: Carbon black (contains 90% dispersant, 10% carbon black as solid content), average particle size 24 nm
・Ion trapping agent: Bismuth-based ion trapping agent ・Antioxidant: Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane

(1) Fluidity: Viscosity and thixotropy index The viscosity (viscosity (25°C), Pa・s) of the liquid resin composition at 25°C was measured using an E-type viscometer (cone angle 3°, rotation speed 10 revolutions/min). Measured using The thixotropic index at 25°C is the ratio of the viscosity at a rotational speed of 2.5 rotations/min to the viscosity at a rotational speed of 10 rotations/min [(viscosity at 2.5 rotations/min)/(10 rotations/min). 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 results obtained are shown in Table 1 or Table 2.

(filling time)
A test piece was prepared by fixing a glass plate (20 mm x 30 mm x 1 mm thick) instead of a semiconductor element onto a glass slide with a gap of 10 μm. This test piece was placed on a hot plate heated to 110°C, and a liquid resin composition was applied to the side (one side) of the glass plate, and the liquid resin composition penetrated between the slide glass and the glass plate and coated the opposite side. The time it took to reach the target was measured.
The results obtained are shown in Table 1 or Table 2.

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

Claims (7)

(A) an epoxy resin, (B) a curing agent, (C) first silica particles having an average particle diameter of 20 nm to 75 nm that have been surface-treated with a silane coupling agent having a glycidyl group, and (D) an average particle diameter includes second silica particles of 0.4 μm to 1.8 μm ,
The curing agent (B) includes an amine curing agent,
The content of volatile matter is 5% by mass or less,
The total proportion of the first silica particles (C) and the second silica particles (D) is 50% by mass to 75% by mass,
The mass-based ratio of the (C) first silica particles and the (D) second silica particles ((D) second silica particles/(C) first silica particles) is 5 to 13.4. and
The ratio of the average particle diameter of the (C) first silica particles to the average particle diameter of the (D) second silica particles ((D) average particle diameter of the second silica particles/(C) the first A liquid resin composition in which the average particle diameter of silica particles is 7 to 10 . The liquid resin composition according to claim 1, wherein the epoxy resin (A) has a viscosity at 25°C of 1000 Pa·s or less. The liquid resin composition according to claim 1 or 2, containing an ion trapping agent. The liquid resin composition according to any one of claims 1 to 3, which contains a curing accelerator. The liquid resin composition according to any one of claims 1 to 4, which contains an antioxidant. 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 claims 1 to 5, disposed in a gap between the substrate and the electronic component;
An electronic component device comprising: A substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer are prepared using the liquid resin composition according to any one of claims 1 to 5. A method for manufacturing an electronic component device, comprising a step of sealing the electronic component device.