WO2022239554A1

WO2022239554A1 - Resin composition for underfill, and electronic component device and production method therefor

Info

Publication number: WO2022239554A1
Application number: PCT/JP2022/015660
Authority: WO
Inventors: 大輝古池
Original assignee: 昭和電工マテリアルズ株式会社
Priority date: 2021-05-12
Filing date: 2022-03-29
Publication date: 2022-11-17
Also published as: CN117337486A; JPWO2022239554A1; TW202243913A

Abstract

A resin composition for underfills which comprises an epoxy resin, a hardener, an inorganic filler, and one or more silicone compounds including a polyglycerin-modified silicone compound and/or a polyester-modified silicone compound.

Description

RESIN COMPOSITION FOR UNDERFILL, ELECTRONIC COMPONENT DEVICE, AND MANUFACTURING METHOD THEREOF

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

Conventionally, resins have been mainly used as encapsulants for encapsulating semiconductor elements such as transistors and ICs (Integrated Circuits) from the standpoint of productivity and cost. Among them, epoxy resins are widely used because of their excellent balance of properties required for encapsulants, such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products. ing.

2. Description of the Related Art In recent years, with the miniaturization and thinning of electronic component devices in which semiconductor elements are encapsulated, so-called bare chip mounting, in which bare chips are directly mounted on wiring boards, has become mainstream. Examples of electronic component devices based on bare chip mounting include COB (Chip on Board), COG (Chip on Glass), TCP (Tape Carrier Package), and the like. Liquid resin compositions are widely used as sealing materials in these electronic component devices.
In addition, an electronic component device (hereinafter referred to simply as "substrate") in which a semiconductor element is directly bump-connected on a wiring substrate (hereinafter also simply referred to as "substrate") whose substrate is ceramic, glass/epoxy resin, glass/imide resin, polyimide film, etc. In the flip chip), a sealing material called an underfill material is used to fill the gap between the bump-connected semiconductor element and the wiring board.
A resin composition used as an underfill material plays an important role in protecting electronic parts from temperature, humidity and mechanical external force.

In recent years, with the development of information technology, electronic devices are becoming smaller, more highly integrated, and more functional. there is Furthermore, due to the miniaturization of electronic equipment, the distance between the connection terminal arranged on the substrate and the semiconductor element has become narrower than before. Therefore, if the resin component seeps into the substrate at the fillet portion of the semiconductor element sealed with the underfill material (hereinafter also referred to as “bleed”), the wiring may be contaminated by the seepage. be.

Here, a liquid encapsulating resin composition containing an epoxy resin, a liquid aromatic amine, a filler, and a liquid silicone compound having a carboxy group or an amino group is disclosed in order to improve bleeding defects (for example, Patent Document 1).

JP 2006-219575 A

In the liquid encapsulating resin composition described in Patent Document 1, it is described that bleeding cannot be suppressed when a silicone compound that does not contain a carboxy group or an amino group is used. Therefore, a method for suppressing the bleeding of resin components other than the liquid encapsulating resin composition described in Patent Document 1 is desired.

An object of the present disclosure is to provide an underfill resin composition in which the occurrence of bleeding is suppressed, an electronic component device using this underfill resin composition, and a method for manufacturing the same.

Specific means for achieving the above object are as follows.
<1> An underfill resin composition containing an epoxy resin, a curing agent, an inorganic filler, and a silicone compound containing at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound.
<2> The underfill resin composition according to <1>, wherein the content of the silicone compound is 0.0001% by mass to 1% by mass relative to the total amount of the underfill resin composition.
<3> The underfill resin composition according to <1> or <2>, wherein the silicone compound comprises a polyglycerin-modified silicone compound.
<4> The underfill resin according to any one of <1> to <3>, wherein when the silicone compound contains a polyester-modified silicone compound, the polyester-modified silicone compound contains a polyether-polyester-modified silicone compound. Composition.
<5> The underfill resin composition according to any one of <1> to <4>, wherein the curing agent contains an amine-based curing agent.
<6> 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 underfill resin composition according to any one of <1> to <5> disposed in the gap between the substrate and the electronic component;
An electronic component device comprising:
<7> The underfilling according to any one of <1> to <5>, wherein a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer are combined. A method for manufacturing an electronic component device, comprising a step of sealing using a resin composition.

According to the present disclosure, an underfill resin composition that suppresses the occurrence of bleeding, an electronic component device using this underfill resin composition, and a method for manufacturing the same are provided.

DETAILED DESCRIPTION OF THE INVENTION Embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, which do not limit the present invention.
In the present disclosure, the term "process" includes a process that is independent of other processes, and even if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. .
In the present disclosure, the numerical range indicated using "-" includes the numerical values 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 or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
In the present disclosure, each component may contain multiple types of applicable substances. When 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.
Particles corresponding to each component in the present disclosure may include a plurality of types. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.
In the present disclosure, the term “layer” or “film” refers to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present, and only a part of the region. It also includes the case where it is formed.

<Resin composition for underfill>
The underfill resin composition of the present disclosure includes an epoxy resin, a curing agent, an inorganic filler, and a silicone compound including at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound.

The underfill resin composition of the present disclosure (hereinafter also referred to as "underfill material") is at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound (hereinafter also referred to as "specific modified silicone compound"). Contains silicone compounds containing This suppresses the occurrence of bleeding. The reason for this is presumed as follows. When an underfill material is filled in a gap between an electronic component such as a semiconductor element and a wiring board, polar groups such as hydroxyl groups and ester groups contained in a specific modified silicone compound are adsorbed onto the wiring board. Therefore, the wetting and spreading of the preceding liquid film is suppressed, and the occurrence of bleeding is suppressed.

The underfill material is preferably liquid at room temperature. In the present disclosure, "normal temperature" means 25 ° C., and "liquid" means a substance that exhibits fluidity and viscosity and has a viscosity that is a measure of viscosity of 0.0001 Pa s to 100 Pa s. . In addition, "liquid" means being in a liquid state.

In the present disclosure, viscosity is defined as a value obtained by multiplying a measured value obtained by rotating an EHD rotational viscometer at 25°C for 1 minute at a predetermined number of revolutions by a predetermined conversion factor. The above measured values are obtained for a liquid maintained at 25±1° C. using an EHD rotational viscometer equipped with a cone rotor having a cone angle of 3° and a cone radius of 14 mm. The number of rotations and the conversion factor differ depending on the viscosity of the liquid to be measured. Specifically, the viscosity of the liquid to be measured is roughly estimated in advance, and the rotational speed and the conversion factor are determined according to the estimated value.

In the viscosity measurement, if the estimated value of the viscosity of the liquid to be measured is 0 Pa s or more and less than 1.25 Pa s, the rotation speed is 10 times per minute, the conversion factor is 0.5, and the estimated viscosity is 1 .If the viscosity is 25 Pa s or more and less than 2.5 Pa s, the rotation speed is 5 times per minute, and the conversion factor is 1. If the estimated viscosity value is 2.5 Pa s or more and less than 6.25 Pa s, the rotation speed is 2.5 times per minute and the conversion factor is 2. When the estimated value of the viscosity is 6.25 Pa·s or more and less than 12.5 Pa·s, the rotation speed is 1 time per minute and the conversion factor is 5.

The viscosity of the underfill material is not particularly limited. Above all, from the viewpoint of high fluidity, the viscosity of the underfill material at 25° C. is preferably 0.1 Pa·s to 100.0 Pa·s, more preferably 0.1 Pa·s to 50.0 Pa·s. More preferably, it is 0.1 Pa·s to 30.0 Pa·s.

In addition, as an indicator of the ease of filling the underfill material in a narrow gap of several tens of μm to several hundred μm at around 100° C. to 120° C., the viscosity of the underfill material at 110° C. can be mentioned. . The viscosity of the underfill material at 110° C. is preferably 0.20 Pa·s or less, more preferably 0.15 Pa·s or less. The viscosity of the underfill material at 110° C. is measured by a rheometer AR2000 (manufactured by TA Instruments, aluminum cone 40 mm, shear rate 32.5/sec).

In addition, the underfill material has a thixotropic index [ (Viscosity at 2.5 revolutions/minute)/(Viscosity at 10 revolutions/minute)] is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. When the thixotropic index is within the above range, the fillet formability is further improved. The viscosity and thixotropic index of the underfill material can be set within desired ranges by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, and the like.

The underfill material of the present disclosure contains an epoxy resin, a curing agent, an inorganic filler, and a silicone compound containing a specific modified silicone compound, and may contain other components as necessary.

(Epoxy resin)
The underfill material of the present disclosure contains epoxy resin.
The type of epoxy resin is not particularly limited, and can be selected from those commonly used as materials for underfill materials. An epoxy resin may be used individually by 1 type, or may use 2 or more types together.

Examples of epoxy resins include phenol novolac epoxy resins, novolac epoxy resins such as cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, N,N-diglycidylaniline, N , N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, aromatic glycidylamine-type epoxy resins such as aminophenol-type glycidylamine, phenol aralkyl-type epoxy resins having at least one of a phenylene skeleton or a biphenylene skeleton, phenylene skeletons or biphenylene skeletons Aralkyl-type epoxy resins such as naphthol aralkyl-type epoxy resins having at least one, hydroquinone-type epoxy resins, biphenyl-type epoxy resins, stilbene-type epoxy resins, triphenolmethane-type epoxy resins, triphenolpropane-type epoxy resins, alkyl-modified triphenolmethane type epoxy resins, triazine nucleus-containing epoxy resins, dicyclopentadiene-modified phenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, vinylcyclohexene dioxide, dicyclopentadiene oxide, alicyclic diepoxy-adipate, etc. bifunctional aliphatic epoxy compounds having two epoxy groups in the molecule, such as epoxy resins, alkylene glycol diglycidyl ether, poly(alkylene glycol) diglycidyl ether, alkenylene glycol diglycidyl ether, and the like. For example, epoxy resins may include bisphenol-type epoxy resins, aromatic glycidylamine-type epoxy resins, and naphthalene-type epoxy resins.

Among the above epoxy resins, epoxy resins containing a structure in which a glycidyl structure or a glycidylamine structure is bonded to an aromatic ring are preferable from the viewpoint of improving heat resistance, mechanical properties, and moisture resistance.

From the viewpoint of making the underfill material liquid at room temperature, it is preferable to select the epoxy resin so that the entire epoxy resin is liquid at room temperature. That is, when only one kind of epoxy resin is included, it is preferable that the epoxy resin is liquid at room temperature. In the case of a combination of two or more epoxy resins, all of the two or more epoxy resins may be liquid at room temperature, and a part of the epoxy resin may be solid at room temperature, and the two or more epoxy resins are mixed. The combination may sometimes be liquid at room temperature.
When an epoxy resin that is solid at room temperature is used as the epoxy resin, the content of the solid epoxy resin is preferably 20% by mass or less relative to the entire epoxy resin from the viewpoint of fluidity.

When two or more types of epoxy resins are used, the epoxy resins may be mixed in advance and then mixed with the other components, or the epoxy resins may be mixed with the other components without being mixed with each other.

The content of the epoxy resin in the underfill material is not particularly limited, and is preferably 5% to 60% by mass, more preferably 5% to 50% by mass, based on the entire underfill material. When the content of the epoxy resin is within the above range, the reactivity during curing, the heat resistance and mechanical strength after curing, and the fluidity during sealing tend to be excellent.

The epoxy resin preferably contains a bisphenol-type epoxy resin and an aromatic glycidylamine-type epoxy resin. From the viewpoint of fully exhibiting the performance of these epoxy resins, the total content of the bisphenol-type epoxy resin and the aromatic glycidylamine-type epoxy resin is preferably, for example, 20% by mass or more relative to the total epoxy resin. , more preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 80% by mass or more. The total content of the bisphenol-type epoxy resin and the aromatic glycidylamine-type epoxy resin may be, for example, 90% by mass or less based on the total epoxy resin.

When a bisphenol-type epoxy resin and an aromatic glycidylamine-type epoxy are used together as epoxy resins, there is no particular restriction on the mass ratio (bisphenol-type epoxy resin: aromatic glycidylamine-type epoxy). Bisphenol-type epoxy resin: Aromatic glycidylamine-type epoxy is preferably 20:80 to 95:5, and 40:60 to 90:10, from the viewpoint of heat resistance, adhesiveness and fluidity. is more preferred, and 60:40 to 80:20 is even more preferred.

The epoxy equivalent (molecular weight/number of epoxy groups) of the epoxy resin is not particularly limited, and is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 500 g/eq.

The epoxy equivalent of the epoxy resin shall be the value measured by the method according to JIS K 7236:2009.

It is preferable that the purity of the epoxy resin is high. Specifically, it is preferable that the amount of hydrolyzable chlorine is as small as possible because it is related to the corrosion of aluminum wiring on elements such as ICs. From the viewpoint of obtaining an underfill material with excellent moisture resistance, it is preferably, for example, 500 ppm or less.

Here, the amount of hydrolyzable chlorine is obtained by dissolving 1 g of the sample epoxy resin in 30 mL of dioxane, adding 5 mL of 1 mol / L-KOH (potassium hydroxide) methanol solution and refluxing for 30 minutes, and then by potentiometric titration. The obtained value is used as a scale.

(curing agent)
The underfill material of the present disclosure contains a curing agent.
The type of curing agent is not particularly limited, and can be selected from those commonly used as materials for underfill materials. Curing agents may be used alone or in combination of two or more. Examples of curing agents include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and the like. Among these, an amine-based curing agent is preferable as the curing agent.

There are no particular restrictions on the amine-based curing agent, and for example, two or more of one or more selected from the group consisting of primary amino groups and secondary amino groups (hereinafter also simply referred to as "amino groups") per molecule. A compound containing the amino group is preferable, a compound having 2 to 4 amino groups in one molecule is more preferable, and a compound having two amino groups in one molecule (diamine compound) is more preferable.

From the viewpoint of making the underfill material liquid at room temperature, it is preferable to select the curing agent so that the entire curing agent is liquid at room temperature. That is, when only one type of curing agent is included, the curing agent is preferably liquid at room temperature. In the case of a combination of two or more curing agents, all of the two or more curing agents may be liquid at room temperature, and a portion of the curing agents may be solid at room temperature, and the two or more curing agents are mixed. It may be a combination that becomes a liquid at normal temperature when it is mixed.
When a curing agent that is solid at room temperature is used as the curing agent, the content of the solid curing agent is preferably 20% by mass or less based on the total curing agent from the viewpoint of fluidity.

The compound having an amino group is preferably a compound having an aromatic ring (aromatic amine compound), more preferably an aromatic amine compound that is liquid at room temperature, is liquid at room temperature, and contains More preferably, it is an aromatic amine compound having two amino groups.

Examples of aromatic amine compounds that are liquid at room temperature include diethyltoluenediamines such as 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine, 1,3,5-triethyl- triethyldiaminobenzene such as 2,6-diaminobenzene; diamino such as 3,3′-diethyl-4,4′-diaminodiphenylmethane and 3,5,3′,5′-tetramethyl-4,4′-diaminodiphenylmethane; diphenylmethane and the like.

Among the above compounds, for example, diaminodiphenylmethane and diethyltoluenediamine are preferable from the viewpoint of storage stability. When at least one of diaminodiphenylmethane and diethyltoluenediamine is used as the curing agent, the total content is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total curing agent. , more preferably 80% by mass or more. The upper limit of the total content is not particularly limited, and may be, for example, 100% by mass or less with respect to the entire curing agent.

When an aromatic amine compound that is liquid at room temperature is used as the curing agent, the content is preferably 50% by mass or more, preferably 70% by mass or more, based on the total curing agent, from the viewpoint of sufficiently exhibiting its performance. It is more preferable that the content is 80% by mass or more. The upper limit of the content is not particularly limited, and may be 100% by mass or less with respect to the entire curing agent.

When using an aromatic amine compound as a curing agent, the active hydrogen equivalent of the curing agent is not particularly limited. From the viewpoint of further suppressing the occurrence of bleeding, for example, it is preferably 10 g/mol to 200 g/mol, more preferably 20 g/mol to 100 g/mol, and 30 g/mol to 70 g/mol. More preferred.

The active hydrogen equivalent of the curing agent is a value calculated based on the amine value measured according to JIS K7237:1995.

There is no particular restriction on the equivalent ratio of the epoxy resin to the curing agent in the underfill material (the number of moles of epoxy groups in the epoxy resin/the number of moles of active hydrogen in the curing agent). The number of moles of epoxy groups in the epoxy resin/the number of moles of active hydrogen in the curing agent is preferably, for example, 0.7 to 1.6, more preferably 0.8 to 1, from the viewpoint of suppressing each unreacted amount. 0.4 is more preferred, and 0.9 to 1.2 is even more preferred.

(Inorganic filler)
The underfill material of the present disclosure contains an inorganic filler.
The type of inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide. , beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers having a flame retardant effect may also be used. Inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as composite hydroxides of magnesium and zinc, and zinc borate. Among them, fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, or may use 2 or more types together. Examples of the state of the inorganic filler include powders, beads obtained by spheroidizing powders, fibers, and the like.

The content of the inorganic filler in the underfill material is not particularly limited, but from the viewpoint of the thermal expansion coefficient of the cured product and the fluidity of the underfill material, it should be 40% by mass to 70% by mass with respect to the entire underfill material. is preferred, and 50% by mass to 65% by mass is more preferred.

The inorganic filler may contain silica particles. The average particle size of the silica particles is preferably 0.2 μm to 5 μm, more preferably 0.2 μm to 3 μm, and more preferably 0.3 μm to 1 μm, from the viewpoint of the fluidity and filling properties of the underfill material. more preferably 0.4 μm to 0.8 μm.

The inorganic filler may contain large silica particles with a larger average particle size and small silica particles with a smaller average particle size. The preferred range of the average particle size of the large silica particles is the same as the preferred range of the average particle size of the silica particles described above.

The average particle size of the small-diameter silica particles is preferably 7 nm to 100 nm, more preferably 9 nm to 75 nm. When the average particle size of the small-diameter silica particles is 7 nm or more, the viscosity of the underfill material is less likely to increase, and fluidity tends to be less likely to deteriorate. When the average particle size of the small-diameter silica particles is 100 nm or less, the viscosity of the underfill material tends to be reduced.

The proportion of silica particles or large-sized silica particles in the inorganic filler may be 70% by mass or more, or may be 75% by mass or more. In addition, the proportion of silica particles or large-diameter silica particles in the inorganic filler is not particularly limited as long as it is 100% by mass or less, and may be 99.7% by mass or less, or 99.5% by mass or less. may

The proportion of small-diameter silica particles in the inorganic filler may be 0% by mass, 0.5% by mass or more, or 10% by mass or more. Moreover, the ratio of the small-diameter silica particles in the inorganic filler may be 30% by mass or less, or may be 25% by mass or less.

The average particle size of the inorganic filler can be measured by the following method.
When measuring an inorganic filler having an average particle size of 20 nm or more, a solvent (for example, pure water) is added with a surfactant of 1% to 8% by weight in the range of 1% to 5% by weight of the inorganic filler to be measured. % by mass and vibrated for 30 seconds to 5 minutes in a 110 W ultrasonic cleaner to disperse the inorganic filler. About 3 mL of the dispersion liquid is injected into the measurement cell and measured at 25°C. A laser diffraction particle size distribution meter (LA920, manufactured by Horiba, Ltd.) is used as a measuring device to measure the volume-based particle size distribution. The average particle diameter is obtained as the particle diameter (D50%) when the accumulation from the small diameter side is 50% in the volume-based particle size distribution.
When measuring an inorganic filler having an average particle size of less than 20 nm, the inorganic filler is imaged using an electron microscope or the like, the particle size of each particle is measured, and the particle size of 100 arbitrarily selected particles. may be used as the average particle size of the inorganic filler.
When the measurement sample is a cured product, for example, the ash content obtained as a residue after treating the cured product at a high temperature of 800° C. or higher in a muffle furnace or the like can be measured by the above method.

When using large-sized silica particles and small-sized silica particles as the inorganic filler, the ratio of the average particle size of the small-sized silica particles to the average particle size of the large-sized silica particles (average particle size of large-sized silica particles / average of small-sized silica particles The particle diameter) is preferably 7-120, more preferably 10-110, even more preferably 20-100.

When large-diameter silica particles are used as the inorganic filler, the method for determining the ratio of small-diameter silica particles and large-diameter silica particles in the inorganic filler is not particularly limited. For example, the volume-based particle size distribution (frequency distribution) of the inorganic filler is obtained, and both are divided between the peak corresponding to the small-diameter silica particles and the peak corresponding to the large-diameter silica particles. By dividing the volume of the particles by the total volume of the inorganic filler, the ratio of the small-diameter silica particles and the large-diameter silica particles can be obtained. When the composition of the underfill material is known, it is possible to obtain the ratio of the small-diameter silica particles and the large-diameter silica particles in the inorganic filler from the composition of the underfill material. Note that the calculation method is not limited to the above method.

(silicone compound)
The underfill material of the present disclosure contains a silicone compound containing at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound (specific modified silicone compound).
The type of specific modified silicone compound is not particularly limited, and one type may be used alone, or two or more types may be used in combination. For example, one polyglycerin-modified silicone compound or polyester-modified silicone compound may be used alone or two or more may be used in combination, and one or more polyglycerin-modified silicone compounds and one or more polyester-modified silicone compounds may be combined. may
In the present disclosure, "silicone compound" means a compound having a main chain formed by siloxane bonds.
The silicone compound and the specific modified silicone compound are preferably liquid silicone compounds at 25°C.
In the present disclosure, polyglycerin-modified and polyester-modified silicone compounds are classified as polyglycerin-modified silicone compounds.

The content of the silicone compound in the underfill material is preferably 0.0001% by mass to 1% by mass with respect to the entire underfill material from the viewpoint of suitably suppressing the occurrence of bleeding, and further electronic parts such as semiconductor elements. From the viewpoint of the filling speed of the underfill material into the gap between the wiring board and the wiring board, it is more preferably 0.001% by mass to 0.25% by mass, and 0.005% by mass to 0.15% by mass. is more preferred.

The silicone compound may contain only one of the polyglycerin-modified silicone compound and the polyester-modified silicone compound, or may contain both of them. The silicone compound preferably contains a polyglycerin-modified silicone compound.

The polyglycerin-modified silicone compound is not particularly limited as long as it is a silicone compound having a plurality of structural units derived from glycerin. More preferably, it is a polydimethylsiloxane derivative having a plurality of constitutional units derived from glycerin in at least one of the main chain and the side chain.

The polyglycerin-modified silicone compound may be an alkyl-modified polydimethylsiloxane derivative or a non-alkyl-modified polydimethylsiloxane derivative. From the viewpoint of suitably suppressing the occurrence of bleeding, the polyglycerin-modified silicone compound is preferably a polydimethylsiloxane derivative that is not alkyl-modified.

The polyester-modified silicone compound is not particularly limited as long as it is a silicone compound having a plurality of ester groups (-C(=O)-O-), and is a silicone compound having a plurality of ester groups in at least one of the main chain and the side chain. More preferably, it is a polydimethylsiloxane derivative having a plurality of ester groups in at least one of its main chain and side chains.

When the silicone compound contains a polyester-modified silicone compound, the polyester-modified silicone compound preferably contains a polyether-polyester-modified silicone compound. Polyether-polyester modified silicone compounds include, for example, silicone compounds having structural units derived from ester groups and alkylene glycol in at least one of the main chain and side chains. Alkylene glycols include, for example, ethylene glycol, polypropylene glycol, and combinations thereof.

The polyester-modified silicone compound may be a polydimethylsiloxane derivative that has undergone modification other than polyester modification (eg, ether modification), or may be a polydimethylsiloxane derivative that has not undergone modification other than polyester modification.

The specific modified silicone compound may be a compound represented by the following general formula (1).

In general formula (1), each R ¹ independently represents an organic group having a plurality of constitutional units derived from a hydrocarbon group or glycerin, or an organic group having a plurality of ester groups.
When the compound represented by general formula (1) is a polyglycerin-modified silicone compound, at least one of R ¹ is an organic group having a plurality of constitutional units derived from glycerin.
When the compound represented by general formula (1) is a polyester-modified silicone compound, at least one of R ¹ is an organic group having a plurality of ester groups.
l is 0-100.

In general formula (1), the hydrocarbon group represented by R ¹ includes aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups. The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, and from the viewpoint of availability, for example, it is preferably 1 to 10, more preferably 1 to 5, and 1 to 3. More preferred. Alkyl groups can be straight, cyclic, or branched. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, cyclohexyl and the like. A vinyl group, an allyl group, etc. are mentioned as an alkenyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable, from the viewpoint of availability.
Also, part of R ¹ may be an alkyl group other than a methyl group, the remaining R ¹ may be a methyl group, or all of the R ¹ may be a methyl group.

The structural unit derived from glycerin may be, for example, a structural unit represented by the following formula (2). The polyglycerin-modified silicone compound may have a structure in which a plurality of constitutional units represented by formula (2) are bonded.

Specific examples of the silicone compound having a plurality of structural units derived from glycerin include a compound containing a structure represented by the following formula (3) and a compound containing a structure represented by the following formula (4). In formula (3), n means a number of 2 or more.

There are no particular restrictions on the weight average molecular weight of the specific modified silicone compound. From the viewpoint of further suppressing the occurrence of bleeding, for example, it is preferably from 300 to 10,000, more preferably from 500 to 8,000, and even more preferably from 1,000 to 6,000.
In the present disclosure, the weight average molecular weight is a value determined by conversion using a standard polystyrene calibration curve using gel permeation chromatography.

The viscosity of the specific modified silicone compound, preferably the viscosity of the polyglycerin-modified silicone at 25° C., is not particularly limited, and is preferably, for example, 500 mm ² /s to 50,000 mm ² /s, preferably 1000 mm ² /s. s to 10,000 mm ² /s, more preferably 2000 mm ² /s to 5,000 mm ² /s.
The viscosity of a specific modified silicone compound means kinematic viscosity at 25°C. Viscosity in the present disclosure is a value of kinematic viscosity measured using a capillary viscometer by a method conforming to JIS K7367-1:2002.

Commercially available products may be used as the specific modified silicone compound. Commercial products include KF-6100, KF-6104, KF-6105, KF-6106, etc. manufactured by Shin-Etsu Chemical Co., Ltd., BYK-370, BYK-375, etc. manufactured by BYK-Chemie Japan Co., Ltd. and Softcare GS-G manufactured by Kao Corporation.

The silicone compound may or may not contain a silicone compound other than the specific modified silicone compound.
The silicone compound other than the specific modified silicone compound may be an unmodified silicone compound or a modified silicone compound. Modified silicone compounds include polyether-modified silicone compounds, carboxy-modified silicone compounds, amino-modified silicone compounds, and the like.

The content of the specific modified silicone compound contained in the silicone compound may be 70% by mass to 100% by mass, 80% by mass to 100% by mass, or 90% by mass with respect to the entire silicone compound. % to 100% by mass.

(coupling agent)
The underfill material of the present disclosure may contain a coupling agent.
The coupling agent serves to strengthen the adhesiveness between the resin component and the inorganic filler in the underfill material, or between the resin component and the constituent members of the electronic component device. The coupling agent is not particularly limited, and can be selected from those commonly used as components of underfill materials. Specifically, silane compounds such as aminosilanes, epoxysilanes, mercaptosilanes, alkylsilanes, ureidosilanes, and vinylsilanes having one or more selected from the group consisting of a primary amino group, a secondary amino group and a tertiary amino group. , titanium-based compounds, aluminum chelates, and aluminum/zirconium-based compounds. Among these, from the viewpoint of filling properties, silane compounds are preferred, and epoxysilane is more preferred.

When the underfill material contains a coupling agent, its content is not particularly limited. From the viewpoint of strengthening the interfacial adhesion between the resin component and the inorganic filler and the interfacial adhesion between the resin component and the constituent members of the electronic component device, and from the viewpoint of improving the filling property, for example, the total amount of the underfill material is 0 It is preferably 0.05% to 10% by mass, more preferably 0.2% to 5% by mass, even more preferably 0.4% to 1% by mass.

(other ingredients)
In addition to the above ingredients, the underfill material requires curing accelerators, ion trapping agents, antioxidants, organic solvents, release agents, colorants, rubber particles, leveling agents, antifoaming agents, etc. may be included depending on

- Curing accelerator -
The underfill material of the present disclosure may contain a curing accelerator. The type of curing accelerator is not particularly limited, and known curing accelerators can be used.
Specifically, 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-dibutylamino-1,8- Cycloamidine compounds such as diaza-bicyclo[5.4.0]undecene-7; cycloamidine compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, and 2,3-dimethyl quinone compounds such as benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone; Compounds having intramolecular polarization obtained by adding compounds having π bonds such as phenylmethane and phenolic 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 methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; intramolecular polarization obtained by adding a compound having a π bond such as maleic anhydride, the above quinone compound, diazophenylmethane, and phenolic resin to an organic phosphine compound; Phosphorus compounds having; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate; derivatives of tetraphenylboron salts adducts of phosphine compounds such as triphenylphosphonium-triphenylborane, N-methylmorpholine tetraphenylphosphonium-tetraphenylborate, and tetraphenylboron salts; A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

When the underfill material contains a curing accelerator, the content of the curing accelerator is preferably 0.1% by mass to 8% by mass with respect to the total amount of the epoxy resin and the curing agent.

－Ion trap agent－
The underfill material of the present disclosure may contain ion trapping agents.
The ion trapping agent that can be used in the present disclosure is not particularly limited as long as it is an ion trapping agent commonly used in underfill materials used for manufacturing electronic component devices. Examples of ion trapping agents 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.)

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

In addition, ion trapping agents other than those described above include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like.
An ion trap agent may be used individually by 1 type, or may use 2 or more types together.

When the underfill material contains an ion trapping agent, the content of the ion trapping agent is preferably 1 part by mass or more with respect to 100 parts by mass of the epoxy resin from the viewpoint of achieving sufficient moisture resistance reliability. From the viewpoint of sufficiently exhibiting the effects of the other components, the content of the ion trapping agent is preferably 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin, and is 1 to 10 parts by mass. is more preferable, and 2 parts by mass to 5 parts by mass is even more preferable.

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

-Antioxidant-
The underfill material of the present disclosure may also contain an antioxidant. A conventionally well-known thing can be used as an antioxidant.
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)butyl tane, 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-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine and the like.
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 and the like. .
Amine compound antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, 2,4-bis-(n- octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine and the like.
Among amine compound-based antioxidants, dicyclohexylamine is commercially available under the trade name of D-CHA-T manufactured by Shin Nippon Rika 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.
Phosphorus compound-based antioxidants include trisnonylphenyl phosphite, 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]dioxaphosphepin- 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- 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. Specific examples of antioxidants include compounds containing at least one of a phosphorus atom, a sulfur atom and an amine in the same molecule in addition to a phenolic hydroxy group. There is

When the underfill material contains an antioxidant, the content of the antioxidant is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 10% by mass, based on the total epoxy resin. 5% by mass.

-Organic solvent-
The underfill material of the present disclosure can be blended with an organic solvent as necessary to reduce the viscosity. In particular, when using at least one of a solid epoxy resin and a solid curing agent, it is preferable to blend an organic solvent in order to obtain a liquid resin composition.
The organic solvent is not particularly limited, and 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, and propylene glycol methyl ether acetate, lactone solvents such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone, dimethylacetamide, dimethyl Amide solvents such as formamide, aromatic solvents such as toluene and xylene, etc. may be mentioned, and one type may be used alone, or two or more types may be used in combination. Among these, an organic solvent having a boiling point of 170° C. or higher is preferable from the viewpoint of avoiding bubble formation due to rapid volatilization when curing the underfill material.

The content of volatile matter including organic solvents and the like is not particularly limited as long as it does not form air bubbles when the underfill material is cured, and is preferably 5% by mass or less with respect to the entire underfill material. It is more preferably 1% by mass or less, and even more preferably 0.1% by mass or less. The lower limit of the content of volatile matter including organic solvents and the like is not particularly limited as long as it is 0% by mass or more.
In the present disclosure, the volatile content of the underfill material is calculated based on the weight difference before and after heating the underfill material at 180° C. for 30 minutes.

-Release agent-
The underfill material of the present disclosure may contain a release agent. The type of release agent is not particularly limited, and known release agents can be used. Specific examples include higher fatty acids, carnauba wax and polyethylene wax. The release agent may be used alone or in combination of two or more.
When the underfill material contains a release agent, the content of the release agent is preferably 10% by mass or less with respect to the total amount of the epoxy resin and the curing agent. , 0.5% by mass or more.

-coloring agent-
The underfill material of the present disclosure may contain colorants such as dyes and carbon black. The colorants may be used singly or in combination of two or more.

When conductive particles such as carbon black are used as the colorant, the conductive particles preferably contain 1% by mass or less of particles having a particle diameter of 10 μm or more.
When the underfill material contains conductive particles, the content of the conductive particles is preferably 3% by mass or less with respect to the total amount of the epoxy resin and the curing agent, and is 0.01% to 1% by mass. is more preferable.

-Rubber Particles-
The underfill material may contain rubber particles from the viewpoint of low 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 of styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), acrylic rubber (AR), and the like. Among them, from the viewpoint of heat resistance and moisture resistance, rubber particles containing acrylic rubber are preferable, and core-shell type acrylic rubber particles are more preferable.

Other examples of suitable rubber particles include silicone rubber particles.
Examples of silicone rubber particles include silicone rubber particles obtained by cross-linking linear polyorganosiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane; surfaces of the silicone rubber particles coated with silicone resin; emulsion polymerization; and core-shell polymer particles containing a core of solid silicone particles obtained by the above method 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 underfill material low, it is preferable to use spherical silicone rubber particles.
Silicone rubber particles are commercially available from Dow Corning Toray Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., and the like.

When the underfill material contains rubber particles, the average particle size of the rubber particles is preferably fine in order to uniformly modify the underfill material. The average particle size 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 size of the rubber particles is 0.05 μm or more, the dispersibility in the underfill material tends to be further improved. When the volume average particle diameter of the rubber particles is 10 μm or less, the effect of reducing stress tends to be further improved, the permeability and fluidity of the underfill material into fine gaps are improved, and voids and unfilling are reduced. It tends to be difficult to invite.
The average particle size of rubber particles is measured using the same method as for inorganic fillers.
When the underfill material contains rubber particles, the rubber particle content is preferably 3% to 30% by mass, more preferably 5% to 28% by mass, based on the total epoxy resin. It is more preferably 10% by mass to 25% by mass.

<Usage of underfill material>
The underfill material can be applied, for example, to a semiconductor device on which electronic components to be described later are mounted.
Further, in recent years, along with the speeding up of semiconductor devices, there are cases where an interlayer insulating film with a low dielectric constant is formed in semiconductor devices. This interlayer insulating film has a weak mechanical strength and is easily destroyed by external stress, so failures are likely to occur. Since this tendency becomes more conspicuous as the size of the semiconductor element increases, there is a demand for reducing the stress caused by the underfill material.
According to the underfill material of the present disclosure, a flip chip connection type electronic component device mounted with a semiconductor element having a size of 2 mm or more on the long side and having an interlayer insulating film with a dielectric constant of 3.0 or less can also provide excellent reliability.
In addition, it exhibits good fluidity and fillability even for flip-chip connection where the distance between the bump connection surface between the wiring board constituting the electronic component and the semiconductor element is 200 μm or less, and the reliability of moisture resistance, thermal shock resistance, etc. It is possible to provide an electronic component device that is also excellent in terms of performance.

<Method for preparing underfill material>
The underfill material is, for example, an epoxy resin, a curing agent, an inorganic filler, a specific silicone compound, and other components that are used as necessary, all together or separately, while being subjected to heat treatment as necessary, and stirred and melted. , mixing, dispersing, or the like. Equipment for mixing, stirring, dispersing, etc. of these components is not particularly limited, and includes a laikai machine equipped with a stirring device, a heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like. mentioned. The underfill material can be obtained by mixing and kneading the above components using these devices, and defoaming as necessary.
As the silica particles, a mixture in which silica particles are mixed in advance with an epoxy resin may be used for the purpose of improving the dispersibility of the particles.

<Electronic parts equipment>
An electronic component device of the present disclosure includes a substrate having a circuit layer, an electronic component disposed on the substrate and electrically connected to the circuit layer, and a book disposed in a gap between the substrate and the electronic component. and a cured product of the disclosed underfill material. The electronic component device of the present disclosure can be obtained by sealing an electronic component with the underfill material of the present disclosure. By sealing the electronic component with the underfill material, the electronic component device of the present disclosure has excellent reliability.

As electronic component devices, semiconductor elements, transistors, diodes, active elements such as thyristors, capacitors, etc. , resistors, resistor arrays, coils, and passive elements such as switches are mounted, and electronic component devices obtained by sealing necessary portions with the underfill material of the present disclosure can be mentioned.
In particular, an electronic component device in which a semiconductor element is flip-chip bonded to wiring formed on a rigid wiring board, a flexible wiring board, or glass by bump connection is one of the targets to which the underfill material 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 underfill material of the present disclosure is useful as an underfill material for flip chips that require high reliability. In the field of flip chips to which the underfill material of the present disclosure is particularly preferably applied, not only the conventional lead-containing solder used as the bump material for connecting the wiring board and the semiconductor element, but also Sn—Ag—Cu A case of lead-free solder such as a system is also included. The underfill material of the present disclosure tends to be able to maintain good reliability even for a flip chip in which bump connections are made using lead-free solder, which is physically more fragile than conventional lead solder. Also, when a chip scale package such as a wafer level CSP (Chip Size Package) is mounted on a substrate, there is a tendency that reliability can be improved by applying the underfill material of the present disclosure.

<Method for manufacturing electronic component device>
A method of manufacturing an electronic component device according to the present disclosure includes sealing a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer using the underfill material according to the present disclosure. It has a step of stopping.
There is no particular limitation on the process of sealing a substrate having a circuit layer and an electronic component using the underfill material of the present disclosure. For example, after connecting an electronic component and a substrate having a circuit layer, an underfill material is applied to the gap between the electronic component and the substrate using capillary action, and then the underfill material undergoes a curing reaction. Also, when the underfill material of the present disclosure is applied to the surface of at least one of the substrate having the circuit layer and the electronic component first, and the electronic component is connected to the substrate by thermocompression, the electronic component and the substrate are connected and underfilled. A pre-coating method in which the curing reaction of the filler material and the curing reaction of the filler material are performed together can be mentioned.
Methods for applying the underfill material include a casting method, a dispensing method, a printing method, and the like.

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

The present invention will be described below based on examples, but the present invention is not limited to the following examples.

[Preparation of underfill material]
The components shown in Tables 1 and 2 were blended in the amounts (parts by mass) shown in Tables 1 and 2, kneaded and dispersed using a three-roll mill and a vacuum crusher, and the underfills of Examples and Comparative Examples were obtained. material was prepared. Details of each material shown in Table 1 are as follows. A blank (-) in Table 1 indicates that it is not blended.

Epoxy resin 1: Liquid bifunctional epoxy resin with an epoxy equivalent of 160 g/mol obtained by epoxidizing bisphenol F Epoxy resin 2: Trifunctional liquid epoxy resin with an epoxy equivalent of 95 g/mol obtained by epoxidizing aminophenol Epoxy Resin 3: Liquid bifunctional epoxy resin with an epoxy equivalent of 143 g/mol obtained by epoxidizing naphthalene Curing agent 1: Diethyltoluenediamine with an active hydrogen equivalent of 45 g/mol Curing agent 2: Diethyldiamino with an active hydrogen equivalent of 63 g/mol Diphenylmethane Inorganic filler: spherical fused silica with an average particle size of 0.5 μm Coloring agent: carbon black Silicone compound 1: KF-6100 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25° C.: 40,000 mm ² /s , modified with polyglycerin)
・Silicone compound 2: KF-6104 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C.: 4,000 mm ² / s, modified with polyglycerin)
・Silicone compound 3: KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C.: 4,000 mm ² / s, polyglycerin-modified and alkyl-modified)
・ Silicone compound 4: KF-6106 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25 ° C.: 3,500 mm ² / s, modified with polyglycerin)
・ Silicone compound 5: BYK-370 (manufactured by BYK-Chemie Japan Co., Ltd., kinematic viscosity at 40 ° C.: about 1 ^mm / s, polyester modification)
・ Silicone compound 6: BYK-375 (manufactured by BYK-Chemie Japan Co., Ltd., polyether-polyester modified)
・ Silicone compound 7: BYK-302 (manufactured by BYK-Chemie Japan Co., Ltd., containing no hydroxy group)
・ Silicone compound 8: BYK-326 (manufactured by BYK-Chemie Japan Co., Ltd., containing no hydroxy group)
・ Silicone compound 9: BYK-333 (manufactured by BYK-Chemie Japan Co., Ltd., containing no hydroxy group)
・ Silicone compound 10: BYK-349 (manufactured by BYK-Chemie Japan Co., Ltd., containing no hydroxy group)

[evaluation]
Using the underfill materials prepared in Examples and Comparative Examples, electronic component devices for testing were produced, and bleeding evaluation and filling speed evaluation were performed. The results are shown in Tables 1 and 2.
The specifications of the test electronic component device are as follows. In the test electronic component device, 20 mg of the underfill material was applied to the gap between the substrate and the semiconductor element by a dispensing method under the condition of 110 ° C., and then cured in the air at 150 ° C. for 2 hours to fill the gap. It was produced by sealing.

・ Size of semiconductor element: 10 mm × 10 mm × 0.4 mm thickness ・ Size of substrate: 35 mm × 35 mm × 1 mm thickness ・ Type of substrate (core): E-679FG (G) (manufactured by Showa Denko Materials Co., Ltd., product name )
・ Type of solder resist: SR-7300G (manufactured by Showa Denko Materials Co., Ltd., trade name)
・Gap between substrate and semiconductor element: 50 μm

(1) Exudation (bleed) length on substrate (bleed evaluation)
The vicinity of the portion in contact with the fillet in the substrate of the electronic component device after sealing is observed with a laser microscope (manufactured by Keyence Corporation, Digital microscope VHX-500 (trade name)), and the length of the underfill material exuding (bleed) was measured. It can be determined that the shorter the length of bleeding (bleed), the more suppressed the occurrence of bleeding.
Based on the measurement result of the bleed length in Comparative Example 5, the bleed length in Examples and Comparative Examples was obtained. That is, the bleeding (μm) in Example or Comparative Example/bleeding (μm) in Comparative Example 5 were obtained. Bleed judgment criteria are as follows.
-criterion-
A: Bleed (μm) in Example or Comparative Example/Bleed (μm) in Comparative Example 5 is less than 1.00.
B: Bleed (μm) in Example or Comparative Example/Bleed (μm) in Comparative Example 5 is 1.00.
C: Bleed (μm) in Example or Comparative Example/Bleed (μm) in Comparative Example 5 is greater than 1.00.

(2) Flow test (evaluation of filling speed)
1 mg of the underfill material is injected into the gap between the support member (glass substrate) and the cover glass used as a substitute for electronic parts by a dispensing method under the condition of 110 ° C., and the gap is completely filled with the underfill material. We measured the time (seconds) until the
The specifications of the evaluation sample are as follows. Table 2 shows the relative values of the filling speed obtained as described above in each example when the value in Comparative Example 5 is taken as a reference value of 1.0.

[Specifications of evaluation samples]
・ Size of glass substrate: 76 mm × 26 mm micro slide glass (manufactured by Matsunami Glass Industry Co., Ltd.)
・ Size of cover glass: 20 mm × 20 mm (manufactured by Matsunami Glass Industry Co., Ltd.)
・Gap between substrate and semiconductor element: 25 μm

As shown in Table 1, in Comparative Examples 1 to 4 using a silicone compound that does not contain a hydroxy group (for example, a polyether-modified silicone compound), the bleeding evaluation was worse than in Comparative Example 5 that did not use a silicone compound. .
On the other hand, as shown in Tables 1 and 2, in Examples 1 to 11 in which a predetermined amount of a silicone compound containing at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound was used, Comparative Example 5 in which no silicone compound was used Bleed evaluation was better than

The disclosure of Japanese Patent Application No. 2021-081207 filed on May 12, 2021 is incorporated herein by reference in its entirety.
All publications, patent applications and technical standards mentioned herein are to the same extent as if each individual publication, patent application and technical standard were specifically and individually noted to be incorporated by reference. incorporated herein by reference.

Claims

An underfill resin composition containing an epoxy resin, a curing agent, an inorganic filler, and a silicone compound containing at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound.
The underfill resin composition according to claim 1, wherein the content of the silicone compound is 0.0001% by mass to 1% by mass with respect to the total amount of the underfill resin composition.
The underfill resin composition according to claim 1 or 2, wherein the silicone compound contains a polyglycerin-modified silicone compound.
The underfill resin composition according to any one of claims 1 to 3, wherein when the silicone compound contains a polyester-modified silicone compound, the polyester-modified silicone compound contains a polyether-polyester-modified silicone compound.
The underfill resin composition according to any one of claims 1 to 4, wherein the curing agent contains an amine-based curing agent.
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 underfill resin composition according to any one of claims 1 to 5, which is arranged in the gap between the substrate and the electronic component;
An electronic component device comprising:
The underfill resin composition according to any one of claims 1 to 5, wherein a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer are combined. A method of manufacturing an electronic component device, comprising a step of sealing using