Liquid resin composition, electronic component device, and method for manufacturing the same

Abstract

To provide a liquid resin composition that exhibits excellent filling properties and can suppress the sedimentation of inorganic fillers within gaps. [Solution] The first liquid resin composition contains epoxy resin, a curing agent, an inorganic filler, and a latent viscosity modifier, wherein the content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is less than 50 parts by mass, and when the content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is A parts by mass, and the content of latent viscosity modifier in 100 parts by mass of the total epoxy resin is B parts by mass, the value of A × B is greater than 20 and less than or equal to 120. The second liquid resin composition contains epoxy resin, a curing agent, an inorganic filler, and a latent viscosity modifier, wherein the content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is 50 parts by mass or more, and the content of latent viscosity modifier is 1.5 parts by mass or less in relation to 100 parts by mass of the total epoxy resin.

Description

Technical Field

[0001] The present disclosure relates to a liquid resin composition, an electronic component device, and a method for manufacturing the same.

Background Art

[0002] Conventionally, in the field of element encapsulation of electronic component devices such as transistors and ICs (Integrated Circuits), resin encapsulation has become 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 a balance of various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserted parts. In semiconductor devices with bare chip mounting such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package), liquid resin compositions are widely used as encapsulating materials. In addition, in semiconductor devices (flip chips) formed by directly bump-connecting semiconductor elements onto wiring boards having substrates such as ceramics, glass / epoxy resins, glass / imide resins, and polyimide films, liquid resin compositions for electronic components are used as underfill materials for filling the gap between the bump-connected semiconductor elements and the wiring board. These liquid resin compositions for electronic components play an important role in protecting electronic components from temperature and humidity, mechanical external forces, etc.

[0003] In addition, with the improvement in performance and increase in power consumption of semiconductor devices, higher heat dissipation performance is required for liquid encapsulating materials used to fill the space between elements / substrates than before. In order to improve the heat dissipation performance of semiconductor elements encapsulated with liquid encapsulating materials, it is effective to use alumina as an inorganic filler contained in the liquid encapsulating materials. For example, Patent Document 1 discloses a liquid encapsulating material containing alumina. Also, Patent Document 2 discloses a solid encapsulating material containing alumina.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-108358 [Patent Document 2] Japanese Patent Publication No. 2018-87299 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Through the inventors' research, it was found that when semiconductor elements are sealed with underfill material, the inorganic filler settles, resulting in a non-uniform distribution of the inorganic filler. In particular, this settling phenomenon of the inorganic filler is likely to occur within the gap between the semiconductor element and the wiring substrate. This phenomenon is especially likely to occur when alumina is used as the inorganic filler. When the inorganic filler becomes non-uniform within the gap between the semiconductor element and the wiring substrate, it can cause failures such as cracks when thermal stress is generated in the semiconductor device. This disclosure has been made in view of the above-mentioned prior circumstances, and one embodiment of this disclosure aims to provide a liquid resin composition that has excellent filling properties and can suppress the sedimentation of inorganic fillers in gaps. Another embodiment of this disclosure aims to provide an electronic component device using this liquid resin composition and a method for manufacturing the same. [Means for solving the problem]

[0006] The specific means for achieving the aforementioned objectives are as follows: <1> It contains epoxy resin, a hardening agent, an inorganic filler, and a latent viscosity modifier. The content of glycidylamine-type epoxy resin in the total 100 parts by mass of the epoxy resin is less than 50 parts by mass. A liquid resin composition in which, when the content of the glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is A (parts by mass), and the content of the latent viscosity modifier in 100 parts by mass of the total epoxy resin is B (parts by mass), the value of A × B is greater than 20 and less than or equal to 120. <2> It contains epoxy resin, a hardening agent, an inorganic filler, and a latent viscosity modifier. The content of glycidylamine-type epoxy resin in the total 100 parts by mass of the epoxy resin is 50 parts by mass or more. A liquid resin composition in which the content of the latent viscosity modifier is 1.5 parts by mass or less per 100 parts by mass of the total epoxy resin. <3> It further contains imidazole compounds. <1> or <2> The liquid resin composition described above. <4> When the content of the glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is A (parts by mass), and the content of the latent viscosity modifier in 100 parts by mass of the total epoxy resin is B (parts by mass), the value of A × B is 120 or less. <2> or <3> The liquid resin composition described above. <5> The inorganic filler contains alumina <1> ~ <4> A liquid resin composition according to any one of the following items. <6> The curing agent includes an amine-based curing agent. <1> ~ <5> A liquid resin composition according to any one of the following items. <7> The epoxy resin further comprises a diglycidyl ether type epoxy resin. <1> ~ <6> A liquid resin composition according to any one of the following items. <8> The epoxy resin further comprises a difunctional aliphatic epoxy compound <1> ~ <7> A liquid resin composition according to any one of the following items. <9> The volatile content is 5% by mass or less. <1> ~ <8> A liquid resin composition according to any one of the following items. <10> It is a capillary underfill material. <1> ~ <9> A liquid resin composition according to any one of the following items. <11> A substrate having a circuit layer, An electronic component arranged on the substrate and electrically connected to the circuit layer, Displaced in the gap between the substrate and the electronic component <1> ~ <10> A cured product of a liquid resin composition according to any one of the following items, An electronic component device equipped with the following features. <12> The gap between a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer is <1> ~ <10> A method for manufacturing an electronic component device, comprising the step of sealing it using a liquid resin composition described in any one of the items. [Effects of the Invention]

[0007] According to one embodiment of this disclosure, a liquid resin composition with excellent filling properties and the ability to suppress the sedimentation of inorganic fillers within gaps can be provided. Furthermore, according to another embodiment of this disclosure, an electronic component device using this liquid resin composition and a method for manufacturing the same can be provided. [Brief explanation of the drawing]

[0008] [Figure 1] This is an SEM image showing an example where the inorganic filler has not settled in the thickness direction of the liquid resin composition after heat treatment. [Figure 2] This is an SEM image showing an example where the inorganic filler has settled in the thickness direction of a liquid resin composition after heat treatment. [Modes for carrying out the invention]

[0009] The present disclosure is described in detail below. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including elemental steps, etc.) are not essential unless otherwise explicitly stated. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0010] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described step by step in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other step-by-step descriptions. Further, in the numerical ranges 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 contain a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may contain a plurality of types of particles. When there are a plurality of types of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of types of particles present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" or "film" include not only the case where the layer or film is formed over the entire region when observing the region where the layer or film exists, but also the case where it is formed only in a part of the region.

[0011] <Liquid resin composition> The first liquid resin composition of the present disclosure contains an epoxy resin, a curing agent, an inorganic filler, and a latent viscosity modifier. The content of the glycidylamine type epoxy resin in the total 100 parts by mass of the epoxy resin is less than 50 parts by mass. When the content of the glycidylamine type epoxy resin in the total 100 parts by mass of the epoxy resin is A (parts by mass), and the content of the latent viscosity modifier with respect to the total 100 parts by mass of the epoxy resin is B (parts by mass), the value of A×B exceeds 20 and is 120 or less. The second liquid resin composition of the present disclosure contains an epoxy resin, a curing agent, an inorganic filler, and a latent viscosity modifier. The content of the glycidylamine type epoxy resin in the total 100 parts by mass of the epoxy resin is 50 parts by mass or more, and the content of the latent viscosity modifier is 1.5 parts by mass or less with respect to the total 100 parts by mass of the epoxy resin. In the present disclosure, the first liquid resin composition and the second liquid resin composition of the present disclosure may be collectively referred to as the "liquid resin composition of the present disclosure". In the present disclosure, a latent viscosity modifier refers to a material that has the property of being unlikely to cause an increase in the viscosity of a liquid resin composition in the filling temperature range of the liquid resin composition, while being likely to increase the viscosity of the liquid resin composition in a region higher than the filling temperature range. According to the liquid resin composition of the present disclosure, it has excellent filling properties and can suppress the sedimentation of the inorganic filler in the gap. Although the reason is not clear, it is speculated as follows. Since the liquid resin composition of the present disclosure contains a latent viscosity modifier, when the liquid resin composition is filled into the gap in the filling temperature range, an increase in the viscosity of the liquid resin composition is suppressed, enabling rapid filling. On the other hand, after the liquid resin composition is filled into the gap, by heating the liquid resin composition to a temperature higher than the filling temperature range, the viscosity of the liquid resin composition increases due to the action of the latent viscosity modifier. The increase in the viscosity of the liquid resin composition suppresses the sedimentation of the inorganic filler in the liquid resin composition. In the liquid resin composition of the present disclosure, when the content of the latent viscosity modifier is within a specific range in relation to the content of the epoxy resin, the increase in the viscosity of the liquid resin composition in the filling temperature range tends to be more suppressed. From the above, it is speculated that the liquid resin composition of the present disclosure has excellent filling properties and can suppress the sedimentation of the inorganic filler in the gap.

[0012] Hereinafter, each component constituting the liquid resin composition of the present disclosure will be described. The liquid resin composition of the present disclosure includes an epoxy resin, a curing agent, an inorganic filler, and a latent viscosity modifier, and may contain other components as necessary. [[ID=?]]

[0013] - Epoxy resin - The liquid resin composition of the present disclosure contains an epoxy resin. The epoxy resin 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 can also be used in combination with the liquid epoxy resin. It should be noted that there seems to be a missing ID number in the original text at the position marked with "?". If this is an oversight, please check and correct it if possible to ensure the integrity and accuracy of the translation.Epoxy resins may be used individually or in combination of two or more types.

[0014] Note that liquid epoxy resin refers to 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 is measured using an E-type viscometer EHD type (cone angle 3°, cone diameter 28 mm), with a measurement temperature of 25°C, a sample volume of 0.7 ml, and the rotation speed set according to the expected viscosity of the sample, as shown below, and the measurement taken 1 minute after the start of measurement. (1) When the expected viscosity is 100 Pa·s to 1000 Pa·s: Rotation speed 0.5 revolutions / minute (2) If the expected viscosity is less than 100 Pa·s: Rotation speed 5 revolutions / minute Furthermore, a solid epoxy resin is defined as an epoxy resin that is solid at room temperature (25°C).

[0015] The type of epoxy resin is not particularly limited. Examples of 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; novolac-type epoxy resins, such as orthocresol novolac-type epoxy resins, which are epoxidized novolac resins of phenols and aldehydes; glycidyl ester-type epoxy resins obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; and glycidylamine-type epoxy resins obtained by the reaction of amine compounds such as diaminodiphenylmethane, isocyanuric acid, and aminophenol with epichlorohydrin. Examples of epoxy resins include difunctional aliphatic epoxy compounds having two epoxy groups in their molecule, such as alkylene glycol diglycidyl ether, poly(alkylene glycol) diglycidyl ether, and alkenylene glycol diglycidyl ether.

[0016] The epoxy resin preferably includes at least one epoxy resin selected from the group consisting of naphthalene-type epoxy resin, diglycidyl ether-type epoxy resin, novolac-type epoxy resin, glycidyl ester-type epoxy resin, and glycidylamine-type epoxy resin, and more preferably includes at least one selected from the group consisting of diglycidyl ether-type epoxy resin and glycidylamine-type epoxy resin. Furthermore, from the viewpoint of reducing the viscosity of the liquid resin composition, it is preferable that the epoxy resin contains a bifunctional aliphatic epoxy compound. The epoxy resin preferably comprises at least one epoxy resin selected from the group consisting of naphthalene-type epoxy resin, diglycidyl ether-type epoxy resin, novolac-type epoxy resin, glycidyl ester-type epoxy resin, and glycidylamine-type epoxy resin, and a difunctional aliphatic epoxy compound. It is more preferably comprises at least one epoxy resin selected from the group consisting of diglycidyl ether-type epoxy resin and glycidylamine-type epoxy resin, and a difunctional aliphatic epoxy compound.

[0017] In the first liquid resin composition of this disclosure, the content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is less than 50 parts by mass, preferably 48 parts by mass or less, and more preferably 46 parts by mass or less. The first liquid resin composition of this disclosure does not need to contain glycidylamine-type epoxy resin as the epoxy resin. When the first liquid resin composition of this disclosure contains a glycidylamine-type epoxy resin as the epoxy resin, the content of the glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 35 parts by mass or more. In the first liquid resin composition of this disclosure, the content of the glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is preferably 20 parts by mass or more and less than 50 parts by mass. In the first liquid resin composition of this disclosure, the content of the difunctional aliphatic epoxy compound in 100 parts by mass of the total epoxy resin is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less. The content of the difunctional aliphatic epoxy compound in 100 parts by mass of the total epoxy resin may be 5 parts by mass or more. The content of the difunctional aliphatic epoxy compound in 100 parts by mass of the total epoxy resin is preferably 5 to 20 parts by mass.

[0018] In the second liquid resin composition of this disclosure, the content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is 50 parts by mass or more, preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. In the second liquid resin composition of this disclosure, the content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less. The content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is preferably 50 parts by mass to 100 parts by mass. In the second liquid resin composition of this disclosure, the content of the difunctional aliphatic epoxy compound in 100 parts by mass of the total epoxy resin is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less. The content of the difunctional aliphatic epoxy compound in 100 parts by mass of the total epoxy resin may be 15 parts by mass or more. The content of the difunctional aliphatic epoxy compound in 100 parts by mass of the total epoxy resin is preferably 15 to 50 parts by mass.

[0019] 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 even more preferably 90 g / eq to 320 g / eq. The epoxy equivalent of 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 then performing potentiometric titration with perchloric acid acetic acid standard solution. An indicator may also be used in this titration.

[0020] Commercially available epoxy resins 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 Chemical & Material Co., Ltd., bisphenol A-type epoxy resin (product name: YD-128) manufactured by Nippon Steel Chemical & Material Co., Ltd., naphthalene-type epoxy resin (product name: HP-4032D) manufactured by DIC Corporation, and the product name "Epogose PT (general grade)" (Yokkaichi Gosei Co., Ltd., diglycidyl ether of polytetramethylene glycol, number average molecular weight 700-800). The epoxy resin is not limited to these specific examples. One type of epoxy resin may be used alone, or two or more types may be used in combination. The epoxy resin content is not particularly limited; for example, it is preferably 5% to 30% by mass, more preferably 7% to 28% by mass, and even more preferably 10% to 25% by mass, as a percentage of the solid content of the liquid resin composition.

[0021] -Hardening agent- The liquid resin composition of this disclosure contains a curing agent. The curing agent can be any agent that polymerizes with the epoxy resin, and can be in liquid or solid form as long as the liquid resin composition is fluid at room temperature (25°C). Examples of curing agents include amine-based curing agents, phenol-based curing agents, and acid anhydride-based curing agents. Among these, amine-based curing agents are preferred from the viewpoint of optimizing the curing temperature of the liquid resin composition.

[0022] Examples of amine-based curing agents include linear aliphatic amines, cyclic aliphatic amines, fatty aromatic amines, and aromatic amines. From the viewpoint of heat resistance and electrical properties, aromatic amines are preferred, and it is more preferable that the amino group is directly bonded to the aromatic ring, and that the aromatic amine contains one or two such aromatic rings per molecule. Specifically, amine-based curing agents include diethyltoluenediamine such as m-phenylenediamine, 2,3-diaminotoluene, 3,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, and 2,4-diaminoanisole, which are 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', Examples include aromatic amine curing agents with two aromatic rings, such as 5,5'-tetramethyl-4,4'-diaminodiphenylmethane and 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane; hydrolysis condensates of aromatic amine curing agents; aromatic amine curing agents having a polyether structure, such as polytetramethylene oxide di-p-aminobenzoate and polytetramethylene oxide di-para-aminobenzoate; condensates of aromatic diamines and epichlorohydrins; reaction products of aromatic diamines and styrene; and polycondensates of aromatic amines and formaldehyde.

[0023] Commercially available amine-based curing agents may be used. Specific examples of commercially available amine-based curing agents include those manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard-AA) and Mitsubishi Chemical Corporation (product names: jER Cure® 113, jER Cure® W, etc.), but amine-based curing agents are not limited to these specific examples. Amine-based curing agents may be used individually or in combination of two or more types.

[0024] Examples of acid anhydride-based curing agents include phthalic anhydride, maleic anhydride, methylhymic anhydride, hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chloride anhydride, methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, benzophenonetetracarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, hydrogenated methylnadic anhydride, and various cyclic acid anhydrides such as trialkyltetrahydrophthalic anhydride and dodecenyl succinic anhydride, which are obtained by the Diels-Alder reaction from maleic anhydride and a diene compound and have multiple alkyl groups.

[0025] Examples of phenolic curing agents include novolac resins, phenolic aralkyl resins, biphenyl aralkyl resins, and naphthol aralkyl resins, obtained by condensing or co-condensing at least one compound 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) with an aldehyde compound (e.g., formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde) under an acidic catalyst. The hardening agent may be used alone or in combination of two or more types.

[0026] It is preferable to set the ratio of the number of equivalent units of the functional group of the curing agent (for example, an amino group in the case of an amine-based curing agent, a phenolic hydroxyl group in the case of a phenol-based curing agent, and an acid anhydride group in the case of an acid anhydride-based curing agent) to the number of equivalent units of the epoxy resin (number of equivalent units of curing agent / number of equivalent units of epoxy resin) in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3, and even more preferably in the range of 0.8 to 1.2.

[0027] -Inorganic filler- The liquid resin composition of this disclosure includes an inorganic filler. As the inorganic filler, known or conventional inorganic fillers can be used, and are not particularly limited. Examples of inorganic fillers include silica such as fused silica and crystalline silica, calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fossilite, steatite, spinel, mullite, titania, and other powders, as well as beads formed from these materials and glass fibers. Furthermore, examples of inorganic fillers with flame-retardant properties include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. These inorganic fillers may be used individually or in combination of two or more types. Of these, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. From the viewpoint of achieving high density of the inorganic filler and ensuring fluidity and penetration of the liquid resin composition into fine gaps, a spherical shape is preferred for the inorganic filler.

[0028] When alumina is included as an inorganic filler, the alumina content in the inorganic filler is preferably 50% by volume or more, more preferably 70% by volume or more, and even more preferably 90% by volume or more. The alumina content in the inorganic filler may be 100% by volume.

[0029] The inorganic filler content is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, relative to the total liquid resin composition, from the viewpoint of hygroscopicity, reduction of linear expansion coefficient, improvement of strength, and solder heat resistance. The inorganic filler content may be 80% by mass or less. The inorganic filler content is preferably 60% by mass to 80% by mass.

[0030] The average particle size of the inorganic filler is preferably 0.5 μm to 10 μm, more preferably 1 μm to 6 μm, and even more preferably 1.5 μm to 4 μm. In this disclosure, the average particle size of the inorganic filler refers to the average particle size of alumina when alumina is used alone as the inorganic filler, and to the average particle size of the entire inorganic filler when alumina and other inorganic fillers are used in combination as the inorganic filler.

[0031] The average particle size of inorganic fillers can be measured by the following method. The inorganic filler to be measured is added to a solvent (pure water) in an amount ranging from 0.02% to 0.08% by mass, and the mixture is vibrated in a 110W bath-type ultrasonic cleaner for 1 to 10 minutes to disperse the inorganic filler. Approximately 40 mL of the dispersion is injected into a measurement cell and measured at 25°C. The measurement device used is a laser diffraction particle size analyzer (Horiba, Ltd., LA920 (product name)) to measure the volume-based particle size distribution. The average particle diameter is determined as the particle diameter (D50%) at which the cumulative amount from the smallest diameter side in the volume-based particle size distribution reaches 50%. The refractive index used is that of alumina. If the inorganic filler is a mixture of alumina and other inorganic fillers, the refractive index used is that of alumina.

[0032] -Coupling agent- The liquid resin compositions of this disclosure may optionally contain a coupling agent to enhance the adhesion between the resin and an inorganic filler or between the resin and a component of an electronic component. Known or conventional coupling agents can be used, and are not particularly limited. Examples of coupling agents include silane compounds having at least one selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups, various silane compounds such as epoxysilanes, mercaptosilanes, alkylsilanes, ureidosilanes, and vinylsilanes, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Among these, silane compounds having at least one selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups are preferred as coupling agents.

[0033] -Imidazole compounds- The liquid resin composition of this disclosure may contain an imidazole compound. Imidazole compounds can function as curing accelerators, promoting the curing reaction between the epoxy resin and the curing agent contained in the liquid resin composition. The types of imidazole compounds are not particularly limited. Examples of imidazole compounds include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole.

[0034] The imidazole compound content is preferably 0.1% to 8% by mass relative to the total amount of epoxy resin and curing agent.

[0035] The liquid resin compositions of this disclosure may contain curing accelerators other than imidazole compounds. Examples of other curing accelerators include cycloamidine compounds, tertiary amine compounds, derivatives of tertiary amine compounds, and organophosphine compounds. If the liquid resin composition of this disclosure contains other curing accelerators, the proportion of the imidazole compound in the curing accelerator is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0036] -Latent viscosity modifier- The liquid resin composition of this disclosure contains a latent viscosity modifier. As described above, the latent viscosity modifier is not particularly limited as long as it has the characteristic of not easily causing an increase in the viscosity of the liquid resin composition in the filling temperature range of the liquid resin composition, but easily increasing the viscosity of the liquid resin composition in a range higher than the filling temperature range. Examples of latent viscosity modifiers include latent curing agents for epoxy resins. The latent curing agent may be a latent curing agent in which a component that has the ability to enhance the effect of epoxy resin and curing agent is microencapsulated or blocked. Specific examples of latent viscosity modifiers include Asahi Kasei Corporation's Novacure® HX-3722, HX-3742, HX-3088, and HXA9382HP. Among these, Novacure® HXA9382HP is preferred.

[0037] In the first liquid resin composition of this disclosure, the content of the latent viscosity modifier is such that when A (parts by mass) is the content of glycidylamine-type epoxy resin in 100 parts by mass of total epoxy resin, and B (parts by mass) is the content of the latent viscosity modifier in 100 parts by mass of total epoxy resin, the value of A × B is greater than 20 and less than or equal to 120. When the value of A × B exceeds 20, the settling of inorganic fillers in the voids tends to be suppressed. When the content of the latent viscosity modifier is 120 or less, the deterioration of the fluidity of the liquid resin composition tends to be suppressed. The value of A × B is preferably 25 to 110, more preferably 30 to 100, and even more preferably 35 to 90. In the first liquid resin composition of this disclosure, the content of the latent viscosity modifier may be 0.7 to 5 parts by mass, 0.8 to 4 parts by mass, or 0.9 to 3 parts by mass per 100 parts by mass of the total epoxy resin. In the second liquid resin composition of this disclosure, the content of the latent viscosity modifier is 1.5 parts by mass or less per 100 parts by mass of the total epoxy resin. When the content of the latent viscosity modifier is 1.5 parts by mass or less per 100 parts by mass of the total epoxy resin, deterioration of the fluidity of the liquid resin composition tends to be suppressed. From the viewpoint of suppressing the sedimentation of inorganic fillers in the gaps, the content of the latent viscosity modifier is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more, per 100 parts by mass of the total epoxy resin. The content of the latent viscosity modifier is preferably 0.1 parts by mass to 1.5 parts by mass per 100 parts by mass of the total epoxy resin.

[0038] In the second liquid resin composition of this disclosure, when the content of glycidylamine-type epoxy resin in 100 parts by mass of total epoxy resin is A (parts by mass), and the content of latent viscosity modifier in 100 parts by mass of total epoxy resin is B (parts by mass), the value of A × B is preferably 120 or less, more preferably 110 or less, even more preferably 100 or less, and particularly preferably 90 or less, from the viewpoint of further improving filling properties and suppressing sedimentation of inorganic fillers. The value of A × B is preferably greater than 20, more preferably 25 or more, even more preferably 30 or more, and particularly preferably 35 or more.

[0039] -Ion trapping agent- The liquid resin composition of this disclosure may contain an ion trapping agent. The ion trapping agents usable in this disclosure are not particularly limited as long as they are commonly used ion trapping agents in encapsulating materials used in the manufacture of semiconductor devices. Examples of ion trapping agents include compounds represented by the following general formula (VI-1) or the following general formula (VI-2).

[0040] Mg 1-aAl a (OH)2(CO3) a / 2 ·uH2O (VI-1) (In general formula (VI-1), a satisfies 0 < a ≤ 0.5 and u is a positive number.) BiO b (OH) c (NO3) d (VI-2) (In general formula (VI-2), b satisfies 0.9 ≤ b ≤ 1.1, c satisfies 0.6 ≤ c ≤ 0.8, and d satisfies 0.2 ≤ d ≤ 0.4.)

[0041] The ion trap agent is commercially available. As the compound represented by the general formula (VI-1), for example, "DHT-4A" (trade name, Kyowa Chemical Industry Co., Ltd.) is commercially available. Also, as the compound represented by the general formula (VI-2), for example, "IXE500" (trade name, Toagosei Co., Ltd.) is commercially available.

[0042] In addition, examples of the ion trap agent other than those described above include hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, etc. The ion trap agent may be used alone or in combination of two or more kinds.

[0043] When the liquid resin composition contains an ion trap agent, from the viewpoint of achieving sufficient moisture resistance reliability, the content of the ion trap agent is preferably 1 part by mass or more with respect to 100 parts by mass in total of the epoxy resin. From the viewpoint of fully exerting the effects of other components, the content of the ion trap agent is preferably 15 parts by mass or less, more preferably 1 part by mass to 10 parts by mass, and even more preferably 2 parts by mass to 5 parts by mass with respect to 100 parts by mass in total of the epoxy resin.

[0044] In addition, the average particle diameter of the ion trap agent is preferably 0.1 μm to 3.0 μm, and the maximum particle diameter is preferably 10 μm or less. The average particle diameter of the ion trap agent can be measured in the same manner as in the case of the inorganic filler.

[0045] -Antioxidant- The liquid resin composition of this disclosure may contain an antioxidant. Conventionally known antioxidants can be used. Examples of antioxidants include phenolic compound-based antioxidants, organosulfur compound-based antioxidants, amine compound-based antioxidants, and phosphorus compound-based antioxidants. Antioxidants may be used individually or in combination of two or more types. The antioxidant content is preferably 0.1% to 10% by mass, and more preferably 0.5% to 5% by mass, relative to the total epoxy resin.

[0046] -Organic Solvents- The liquid resin composition of this disclosure may contain organic solvents as needed to reduce viscosity. In particular, when using a solid epoxy resin and a curing agent, it is preferable to incorporate organic solvents to obtain a liquid resin composition. There are no particular restrictions on the organic solvents, and examples include alcohol-based solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol; ketone-based solvents such as acetone and methyl ethyl ketone; glycol ether-based solvents such as ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, and propylene glycol methyl ether acetate; lactone-based solvents such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone; amide-based solvents such as dimethylacetamide and dimethylformamide; and aromatic solvents such as toluene and xylene. One type may be used alone, or two or more types may be used in combination. Among these, organic solvents with a boiling point of 170°C or higher are preferred from the viewpoint of avoiding bubble formation due to rapid volatilization when curing the liquid resin composition.

[0047] The content of volatile components, including organic solvents, is not particularly limited as long as it does not form bubbles when the liquid resin composition is cured. It is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, relative to the total liquid resin composition. In this disclosure, the volatile content 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.

[0048] -Release agent- The liquid resin composition of this disclosure may contain a release agent. The type of release agent is not particularly limited, and known release agents can be used. Specifically, examples include higher fatty acids, carnauba wax, and polyethylene wax. One type of release agent may be used alone, or two or more types may be used in combination. When a liquid resin composition contains a release agent, the release agent content is preferably 10% by mass or less relative to the total amount of epoxy resin and curing agent, and from the viewpoint of exhibiting its effect, it is preferably 0.5% by mass or more.

[0049] -Colorants- The liquid resin composition of this disclosure may contain a coloring agent (e.g., carbon black). The coloring agent may be used alone or in combination of two or more types.

[0050] When using conductive particles such as carbon black as a coloring agent, it is preferable that the content of conductive particles with a particle size of 10 μm or larger is 1% by mass or less. When the liquid resin composition contains conductive particles, the content of conductive particles is preferably 3% by mass or less, and more preferably 0.01% to 1% by mass, relative to the total amount of epoxy resin and curing agent.

[0051] -Rubber particles- The liquid resin composition of this disclosure may contain rubber particles from the viewpoint of reducing the thermal expansion of the cured product. One type of rubber particle may be used alone, or two or more types may be used in combination. Examples of suitable rubber particles include styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic rubber (AR). Among these, rubber particles containing acrylic rubber are preferred from the viewpoint of heat resistance and moisture resistance, and core-shell type acrylic rubber particles are more preferred.

[0052] Another example of suitable rubber particles is silicone rubber particles. Examples of silicone rubber particles include silicone rubber particles obtained by crosslinking linear polyorganosiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane; silicone rubber particles whose surface is coated with silicone resin; and core-shell polymer particles containing a core of solid silicone particles obtained by emulsion polymerization or the like and a shell of an organic polymer such as acrylic resin. The shape of these silicone rubber particles may be amorphous or spherical, but it is preferable to use spherical silicone rubber particles in order to keep the viscosity of the liquid resin composition low. Silicone rubber particles are commercially available from companies such as Toray Dow Corning Silicone Co., Ltd. and Shin-Etsu Chemical Co., Ltd.

[0053] When the liquid resin composition of this disclosure contains rubber particles, the average particle size of the rubber particles is preferably fine in order to uniformly modify the liquid resin composition. The average particle size of the rubber particles is preferably in the range of 0.05 μm to 10 μm, and more preferably in the range of 0.1 μm to 5 μm. When the average particle size of the rubber particles is 0.05 μm or more, the dispersibility in the liquid resin composition tends to improve further. When the average particle size of the rubber particles is 10 μm or less, the stress reduction improvement effect tends to improve further, the penetration into fine gaps and fluidity of the liquid resin composition improve, and the likelihood of voids and unfilled areas tends to decrease. The average particle size of rubber particles is measured using the same method as for inorganic fillers. The rubber particle content is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 5 to 12 parts by mass, per 100 parts by mass of total epoxy resin.

[0054] <Method for preparing liquid resin composition> The liquid resin composition of this disclosure can be obtained, for example, by stirring, melting, mixing, dispersing, etc., an epoxy resin, a curing agent, an inorganic filler, a latent viscosity modifier, and other components used as needed, either together or separately, while applying heat treatment as necessary. The apparatus for mixing, stirring, dispersing, etc., of these components is not particularly limited and includes a mixing machine equipped with a stirring device, a heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. The liquid resin composition can be obtained by mixing, kneading, and degassing the above components as needed using these apparatus.

[0055] The viscosity of the liquid resin composition is not particularly limited. However, 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 even more preferably 10.0 Pa·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).

[0056] Furthermore, when using the liquid resin composition as an underfill material or for other applications, as an indicator of ease of filling when filling narrow gaps of several tens of micrometers to several hundred micrometers in size at around 100°C to 120°C, the viscosity at 110°C is preferably 0.5 Pa·s or less, more preferably 0.4 Pa·s or less, and even more preferably 0.3 Pa·s or less. The viscosity of the liquid resin composition at 110°C is measured using a rheometer HR-2 (manufactured by TA Instruments, with a 25mm aluminum cone and a heating rate of 10°C / min).

[0057] Furthermore, the liquid resin composition preferably has a oscillating index [(viscosity at 2.5 revolutions / min) / (viscosity at 10 revolutions / min)], which is the ratio of the viscosity at a rotation speed of 2.5 revolutions / min to the viscosity at a rotation speed of 10 revolutions / min, measured using an E-type viscometer at 25°C, between 0.3 and 1.5, and more preferably between 0.5 and 1.2. When the oscillating index is within the above range, the filling properties tend to improve further. Note that the viscosity and oscillating index of the liquid resin composition can be set to a desired range by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, etc.

[0058] The curing conditions for the liquid resin composition are not particularly limited, but heating at 80°C to 165°C for 1 minute to 150 minutes is preferred.

[0059] <Electronic Components and Devices> The electronic component apparatus of this disclosure comprises a substrate having a circuit layer, an electronic component disposed on the substrate and electrically connected to the circuit layer, and a cured product of the liquid resin composition of this disclosure disposed in the gap between the substrate and the electronic component. The electronic component apparatus of this disclosure can be obtained by encapsulating the electronic component with the liquid resin composition of this disclosure. Because the electronic component is encapsulated with the liquid resin composition, the electronic component apparatus of this disclosure is highly reliable.

[0060] Examples of electronic component devices include those obtained by mounting electronic components such as semiconductor chips, active elements such as transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, resistor arrays, coils, and switches on a substrate having a circuit layer such as a lead frame, a pre-wired tape carrier, a rigid wiring board, a flexible wiring board, glass, or a silicon wafer, and then sealing the necessary parts with the liquid resin composition of this disclosure. In particular, semiconductor devices to which semiconductor elements are flip-chip bonded by bump connection to wiring formed on rigid wiring boards, flexible wiring boards, or glass are examples of devices to which the liquid resin composition of this 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).

[0061] The liquid resin composition of this disclosure is suitable as a highly reliable underfill material for flip chips (e.g., capillary underfill material). The liquid resin composition of this disclosure is particularly suitable for use in flip chip applications where the bump material connecting the wiring substrate and semiconductor element is not only conventional lead-containing solder, but also lead-free solder such as Sn-Ag-Cu-based solder is used. Even for flip chips with bump connections using lead-free solder, which is physically more brittle than conventional lead solder, the liquid resin composition of this disclosure tends to maintain good reliability. Furthermore, applying the liquid resin composition of this disclosure when mounting chip-scale packages such as wafer-level CSPs (Chip Size Packages) onto a substrate tends to improve reliability. Furthermore, in recent years, with the increasing speed of semiconductor devices, low dielectric constant interlayer insulating films are sometimes formed on semiconductor devices. The liquid resin composition of this disclosure can also be applied to flip-chip connected electronic component devices that incorporate semiconductor devices having such interlayer insulating films. Furthermore, even for flip-chip connections where the distance between the bump connection surface of the wiring board constituting the electronic component and the semiconductor element is, for example, 200 μm or less, it exhibits good fluidity and filling properties, and tends to provide electronic component devices with excellent reliability.

[0062] <Manufacturing method for electronic component devices> A method for manufacturing an electronic component device according to the present disclosure includes a step of sealing the gap between 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 the present disclosure. There are no particular limitations on the process of sealing the gap between a substrate having a circuit layer and an electronic component using the liquid resin composition of this disclosure. For example, there is a post-application method in which, after connecting the electronic component and the substrate having a circuit layer, the liquid resin composition is applied to the gap between the electronic component and the substrate using capillary action, and then the curing reaction of the liquid resin composition is carried out. There is also a pre-application method in which the liquid resin composition of this disclosure is applied to at least one surface of the substrate having a circuit layer and the electronic component, and when the electronic component is connected to the substrate by heat-pressing, the connection of the electronic component and the substrate and the curing reaction of the liquid resin composition are carried out in a single process. Methods for applying the liquid resin composition include casting, dispensing, and printing. [Examples]

[0063] The present disclosure will be described below based on examples, but the present disclosure is not limited to the following examples. In the following examples, parts and % refer to parts by mass and mass %, respectively, unless otherwise specified.

[0064] (Examples 1-5 and Comparative Examples 1-6) Each component was blended to achieve the composition shown in Table 1, and the mixture was kneaded and dispersed using a three-roll mill and a vacuum mill to prepare the liquid resin compositions of Examples 1-5 and Comparative Examples 1-6. In Table 1, the blending units for the curing agent are in terms of equivalent weight relative to the total epoxy resin, and the blending units for the inorganic filler are in terms of the mass-based proportion (mass%) of the inorganic filler to the total liquid resin composition. The blending ratios for other components are also based on mass. Furthermore, the "A×B value" in Table 1 represents the A×B value when A (parts by mass) is the content of glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin, and B (parts by mass) is the content of latent viscosity modifier in 100 parts by mass of the total epoxy resin.

[0065] The materials used in the preparation of the liquid resin composition and their abbreviations are shown below. (Epoxy resin) • Epoxy resin 1: Bisphenol F type epoxy resin (diglycidyl ether type epoxy resin, epoxy equivalent: 160 g / eq) • Epoxy resin 2: Aminophenol-type epoxy resin (glycidylamine-type epoxy resin, epoxy equivalent: 96g / eq) • Epoxy resin 3: Difunctional aliphatic epoxy compound (epoxy equivalent: 138 g / eq)

[0066] (Hardening agent) • Hardener 1: Diethyltoluenediamine • Hardener 2: Polycondensate of formaldehyde such as 3,3'-diethyl-4,4'-diaminodiphenylmethane and 2-ethylaniline

[0067] • Rubber particles: Silicone rubber particles • Latent viscosity modifier: Novacure HXA9382HP (Asahi Kasei Corporation) • Curing accelerator: Imidazole compound (2-phenyl-4-methyl-5-hydroxymethylimidazole) • Coloring agent: Carbon black • Inorganic filler: Alumina (average particle size: 2.5 μm to 3.0 μm, specific gravity: 3.5 to 4.0)

[0068] [Table 1]

[0069] -Measurement of viscosity profile at increased temperature- The viscosity profile of each liquid resin composition was measured using a rheometer HR-2 (manufactured by TA Instruments, with a 25mm aluminum cone and a heating rate of 10°C / min). The viscosity of each liquid resin composition at 100°C, 110°C, 120°C, and 165°C is shown in Tables 2 and 3.

[0070] [Table 2]

[0071] [Table 3]

[0072] -Evaluation of filling properties- A test specimen was prepared by creating a 25 μm gap on a glass slide and fixing a glass plate (20 mm × 20 mm × 1 mm thick) in place of a semiconductor element. The test specimen was placed on a hot plate heated to 100°C, and the liquid resin composition was applied to one side of the glass plate, filling the space between the glass slide and the glass plate. Visual inspection was performed to determine whether the liquid resin composition reached the side of the glass plate opposite to the side it was directed to. The results are shown in Tables 2 and 3. If the composition reached the opposing side, it was indicated as "flowing" in Tables 2 and 3. If it did not reach the opposing side, it was indicated as "stopping" in Tables 2 and 3.

[0073] -Evaluation of subsidence suppression- The same test specimens used for the filling performance evaluation were employed. Each liquid resin composition was filled into the test specimens described above, using the same method as for "fillability evaluation," except for the filling temperature. The filling temperatures for each example and comparative example were as described in Table 2 or Table 3. Each liquid resin composition was subjected to a heat treatment at 165°C for 2 hours. SEM imaging was performed on the center of each test specimen after heat treatment (the midpoint in the filling direction and the midpoint in the filling width). The imaging conditions were set to x4000 magnification. Based on the obtained SEM images, the presence or absence of sedimentation of the inorganic filler was determined as follows. At the center of each specimen in the SEM image, we observed whether there was a gradient in the dispersion of the inorganic filler in the thickness direction of the liquid resin composition after heat treatment. If there was no gradient in the dispersion of the inorganic filler in the thickness direction (i.e., the inorganic filler had not settled), it was evaluated as "none," and if there was a gradient in the dispersion of the inorganic filler in the thickness direction (i.e., the inorganic filler had settled), it was evaluated as "present." The results obtained are shown in Table 2 or Table 3. Here, Figure 1 shows an SEM image illustrating an example where the inorganic filler has not settled, and Figure 2 shows an SEM image illustrating an example where the inorganic filler has settled.

[0074] As is clear from the results shown in Table 2 or Table 3, the liquid resin composition of the example exhibited excellent filling properties and was able to suppress the sedimentation of the inorganic filler within the gaps. On the other hand, the liquid resin composition of the comparative example had poor filling properties or the inorganic filler sedimented.

Claims

1. It contains epoxy resin, a hardening agent, an inorganic filler, and a latent viscosity modifier. The content of glycidylamine-type epoxy resin in the total 100 parts by mass of the epoxy resin is less than 50 parts by mass. A liquid resin composition in which, when the content of the glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is A (parts by mass), and the content of the latent viscosity modifier in 100 parts by mass of the total epoxy resin is B (parts by mass), the value of A × B is greater than 20 and less than or equal to 120.

2. It contains epoxy resin, a hardening agent, an inorganic filler, and a latent viscosity modifier. The content of glycidylamine-type epoxy resin in the total 100 parts by mass of the epoxy resin is 50 parts by mass or more. A liquid resin composition in which the content of the latent viscosity modifier is 1.5 parts by mass or less per 100 parts by mass of the total epoxy resin.

3. The liquid resin composition according to claim 1 or claim 2, further comprising an imidazole compound.

4. The liquid resin composition according to claim 2, wherein when the content of the glycidylamine-type epoxy resin in 100 parts by mass of the total epoxy resin is A (parts by mass), and the content of the latent viscosity modifier in 100 parts by mass of the total epoxy resin is B (parts by mass), the value of A × B is 120 or less.

5. The liquid resin composition according to claim 1 or claim 2, wherein the inorganic filler comprises alumina.

6. The liquid resin composition according to claim 1 or claim 2, wherein the curing agent comprises an amine-based curing agent.

7. The liquid resin composition according to claim 1 or claim 2, further comprising a diglycidyl ether type epoxy resin as the epoxy resin.

8. The liquid resin composition according to claim 1 or claim 2, wherein the epoxy resin further comprises a difunctional aliphatic epoxy compound.

9. The liquid resin composition according to claim 1 or claim 2, wherein the volatile content is 5% by mass or less.

10. A liquid resin composition according to claim 1 or claim 2, which is a capillary underfill material.

11. A substrate having a circuit layer, An electronic component arranged on the substrate and electrically connected to the circuit layer, A cured product of the liquid resin composition according to claim 1 or claim 2 is disposed in the gap between the substrate and the electronic component, An electronic component device equipped with the following features.

12. A method for manufacturing an electronic component device, comprising the step of sealing the gap between 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 described in claim 1 or claim 2.

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