Resin composition for underfill, electronic component device, and method for manufacturing the same.

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

[Technical Field]

[0001] The present invention relates to a resin composition for underfill, an electronic component device, and a method for manufacturing the same. [Background technology]

[0002] Traditionally, resins have been primarily used as encapsulants for semiconductor devices such as transistors and ICs (Integrated Circuits) due to their productivity and cost-effectiveness. Among these, epoxy resins are widely used because they offer an excellent balance of various properties required for encapsulants, including workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

[0003] In recent years, with the miniaturization and thinning of electronic components and devices that enclose semiconductor elements, so-called bare chip mounting, where bare chips are directly mounted onto a wiring board, has become mainstream. Examples of electronic components and devices using this bare chip mounting method include COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package). In these electronic components and devices, liquid resin compositions are widely used as encapsulants. Furthermore, in electronic component devices (flip chips) in which semiconductor elements are directly bump-connected onto a wiring board (hereinafter also simply referred to as "substrate") made of ceramic, glass / epoxy resin, glass / imide resin, polyimide film, etc., a sealing material called an underfill material is used to fill the gap between the bump-connected semiconductor elements and the wiring board. The resin compositions used as underfill materials play an important role in protecting electronic components from temperature, humidity, and mechanical forces.

[0004] In recent years, with the advancement of information technology, electronic devices have become even smaller, more integrated, and more multifunctional, leading to smaller bump diameters, narrower pitches, and narrower gaps due to the increased number of pins. Furthermore, the miniaturization of electronic devices has resulted in narrower spacing between connection terminals and semiconductor elements on the circuit board compared to the past. As a result, if resin components seep into the circuit board at the fillet portion of a semiconductor element sealed with underfill material (hereinafter also referred to as "bleeding"), the wiring may become contaminated by this seepage.

[0005] Here, a liquid encapsulating resin composition is disclosed that includes an epoxy resin, a liquid aromatic amine, a filler, and a liquid silicone compound having a carboxyl group or an amino group, in order to improve bleeding defects (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2006-219575 [Overview of the project] [Problems that the invention aims to solve]

[0007] Patent Document 1 describes that when a silicone compound without carboxyl and amino groups is used in the liquid encapsulation resin composition, bleeding cannot be suppressed. Therefore, there is a need for a method to suppress the bleeding of resin components other than the liquid encapsulation resin composition described in Patent Document 1.

[0008] This disclosure aims to provide an underfill resin composition that suppresses the occurrence of bleeding, as well as an electronic component device using this underfill resin composition and a method for manufacturing the same. [Means for solving the problem]

[0009] The specific means for achieving the aforementioned objectives are as follows: <1> An underfill resin composition comprising 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 content of the silicone compound is 0.0001% to 1% by mass relative to the total amount of the underfill resin composition. <1> The resin composition for underfill described above. <3> The silicone compound includes a polyglycerin-modified silicone compound. <1> or <2> The resin composition for underfill described above. <4> If the silicone compound includes a polyester-modified silicone compound, the polyester-modified silicone compound includes a polyether-polyester-modified silicone compound. <1> ~ <3> An underfill resin composition as described in any one of the following. <5> The curing agent includes an amine-based curing agent. <1> ~ <4> An underfill resin composition as described in any one of the following. <6> 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> ~ <5> A cured product of an underfill resin composition described in any one of the following, An electronic component device equipped with the following features. <7> A substrate having a circuit layer, and electronic components disposed on the substrate and electrically connected to the circuit layer, <1> ~ <5> A method for manufacturing an electronic component device, comprising the step of sealing it using an underfill resin composition described in any one of the following. [Effects of the Invention]

[0010] This disclosure provides an underfill resin composition that suppresses the occurrence of bleeding, as well as an electronic component device using this underfill resin composition and a method for manufacturing the same. [Modes for carrying out the invention]

[0011] Hereinafter, embodiments for implementing the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) 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 "step" includes, in addition to steps independent of other steps, the step even if it cannot be clearly distinguished from other steps as long as the purpose of the step is achieved. In the numerical range indicated by "~" in the present disclosure, the numerical values described before and after "~" are included as the minimum value and the maximum value, 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. Also, 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. The particles corresponding to each component in the present disclosure may contain a plurality of types. When there are a plurality of types of particles corresponding to each component in the composition, the particle diameter of each component means a value for the mixture of the plurality of types of particles present in the composition, unless otherwise specified. In the present disclosure, the term "layer" or "film" includes not only the case where it is formed over the entire region where the layer or film exists but also the case where it is formed only in a part of the region when observing the region where the layer or film exists.

[0012] <Underfill resin composition> The underfill resin composition of the present disclosure includes an epoxy resin, a curing agent, an inorganic filler, and a silicone compound containing at least one of a polyglycerol-modified silicone compound and a polyester-modified silicone compound.

[0013] The underfill resin composition of this disclosure (hereinafter also referred to as "underfill material") contains a silicone compound comprising at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound (hereinafter also referred to as "specific modified silicone compound"). This suppresses the occurrence of bleeding. The reason for this is presumed to be as follows: When filling the gap between electronic components such as semiconductor elements and a wiring substrate with the underfill material, polar groups such as hydroxyl groups and ester groups contained in the specific modified silicone compound are adsorbed onto the wiring substrate. Therefore, the wetting spread of the preceding liquid film is suppressed, and the occurrence of bleeding is suppressed.

[0014] The underfill material is preferably liquid at room temperature. In this disclosure, "room temperature" means 25°C, and "liquid" means a substance that exhibits fluidity and viscosity, and whose viscosity, a measure of viscosity, is between 0.0001 Pa·s and 100 Pa·s. Furthermore, "liquid state" means being in a liquid state.

[0015] In this disclosure, viscosity is defined as the value obtained by multiplying the measurement taken when an EHD-type rotational viscometer is rotated at a predetermined rotational speed for 1 minute at 25°C by a predetermined conversion factor. The above measurement is obtained using an EHD-type rotational viscometer equipped with a cone rotor having a cone angle of 3° and a cone radius of 14 mm, for a liquid maintained at 25±1°C. The rotational speed and conversion factor vary depending on the viscosity of the liquid being measured. Specifically, the viscosity of the liquid being measured is roughly estimated in advance, and the rotational speed and conversion factor are determined according to the estimated value.

[0016] In viscosity measurement, if the estimated viscosity of the liquid being measured is between 0 Pa·s and less than 1.25 Pa·s, the rotation speed is set to 10 revolutions per minute and the conversion factor to 0.5. If the estimated viscosity is between 1.25 Pa·s and less than 2.5 Pa·s, the rotation speed is set to 5 revolutions per minute and the conversion factor to 1. If the estimated viscosity is between 2.5 Pa·s and less than 6.25 Pa·s, the rotation speed is set to 2.5 revolutions per minute and the conversion factor to 2. If the estimated viscosity is between 6.25 Pa·s and less than 12.5 Pa·s, the rotation speed is set to 1 revolution per minute and the conversion factor to 5.

[0017] The viscosity of the underfill material is not particularly limited. However, 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, and even more preferably 0.1 Pa·s to 30.0 Pa·s.

[0018] Furthermore, the viscosity of the underfill material at 110°C is used as an indicator of the ease of filling narrow gaps of several tens to several hundreds of micrometers in size when filling with underfill material at around 100°C to 120°C. The viscosity of the underfill material at 110°C is preferably 0.20 Pa·s or less, and more preferably 0.15 Pa·s or less. The viscosity of the underfill material at 110°C is measured using a rheometer AR2000 (manufactured by TA Instruments, with a 40 mm aluminum cone and a shear rate of 32.5 / sec).

[0019] Furthermore, the underfill material 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 0.5 and 1.5, and more preferably between 0.8 and 1.2. Fillet formation is further improved when the oscillating index is within the above range. Note that the viscosity and oscillating index of the underfill material can be set to a desired range by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, etc.

[0020] The underfill material of this disclosure comprises an epoxy resin, a curing agent, an inorganic filler, and a silicone compound including a specific modified silicone compound, and may optionally contain other components.

[0021] (Epoxy resin) The underfill material of this disclosure contains epoxy resin. The type of epoxy resin is not particularly limited and can be selected from those commonly used as underfill materials. One type of epoxy resin may be used alone, or two or more types may be used in combination.

[0022] Examples of epoxy resins include novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins, bisphenol-type epoxy resins such as bisphenol A-type epoxy resins and bisphenol F-type epoxy resins, aromatic glycidylamine-type epoxy resins such as N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane-type glycidylamine, and aminophenol-type glycidylamine, aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins having at least one of a phenylene skeleton or a biphenylene skeleton, naphthol aralkyl-type epoxy resins having at least one of a phenylene skeleton or a biphenylene skeleton, and hydroquinone-type epoxy resins. Examples include 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-adipade and other alicyclic epoxy resins, and difunctional aliphatic epoxy compounds having two epoxy groups in the molecule, such as alkylene glycol diglycidyl ether, poly(alkylene glycol) diglycidyl ether, and alkenylene glycol diglycidyl ether. For example, the epoxy resin may include bisphenol-type epoxy resins, aromatic glycidylamine-type epoxy resins, and naphthalene-type epoxy resins.

[0023] Among the epoxy resins mentioned above, epoxy resins containing a structure in which a glycidyl structure or a glycidylamine structure is bonded to an aromatic ring are preferred from the viewpoint of improving heat resistance, mechanical properties, and moisture resistance.

[0024] From the viewpoint of making the underfill material liquid at room temperature, it is preferable to select epoxy resins such that the epoxy resin as a whole becomes liquid at room temperature. That is, if only one type of epoxy resin is included, it is preferable that the epoxy resin is liquid at room temperature. If two or more types of epoxy resins are used as a combination, all two or more epoxy resins may be liquid at room temperature, or some of the epoxy resins may be solid at room temperature, and the combination may become liquid at room temperature when the two or more epoxy resins are mixed. When using an epoxy resin that is solid at room temperature, the content of the solid epoxy resin is preferably 20% by mass or less of the total epoxy resin, from the viewpoint of fluidity.

[0025] When using two or more types of epoxy resins, the epoxy resins may be mixed together beforehand and then mixed with the other components, or they may be mixed with the other components without mixing the epoxy resins together first.

[0026] The epoxy resin content in the underfill material is not particularly limited, but is preferably 5% to 60% by mass of the total underfill material, and more preferably 5% to 50% by mass. When the epoxy resin content is within the above range, the reactivity during curing, heat resistance and mechanical strength after curing, and fluidity during sealing tend to be excellent.

[0027] 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 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more, relative to the total epoxy resin. The total content of the bisphenol-type epoxy resin and the aromatic glycidylamine-type epoxy resin may also be, for example, 90% by mass or less relative to the total epoxy resin.

[0028] When using a combination of bisphenol-type epoxy resin and aromatic glycidylamine-type epoxy as epoxy resins, there are no particular restrictions on their mass ratio (bisphenol-type epoxy resin: aromatic glycidylamine-type epoxy). From the viewpoint of heat resistance, adhesion, and fluidity, the ratio of bisphenol-type epoxy resin to aromatic glycidylamine-type epoxy is preferably, for example, 20:80 to 95:5, more preferably 40:60 to 90:10, and even more preferably 60:40 to 80:20.

[0029] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited, but is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.

[0030] The epoxy equivalent of the epoxy resin shall be the value measured according to the method conforming to JIS K 7236:2009.

[0031] The purity of the epoxy resin is preferably high. Specifically, the amount of hydrolyzable chlorine is particularly preferable to be low, as it is related to the corrosion of aluminum wiring on ICs and other devices. From the viewpoint of obtaining an underfill material with excellent moisture resistance, for example, it is preferable that the purity be 500 ppm or less.

[0032] Here, the amount of hydrolyzable chlorine is measured by dissolving 1 g of epoxy resin sample in 30 mL of dioxane, adding 5 mL of 1 mol / L-KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then determining the value by potentiometric titration.

[0033] (Hardening agent) The underfill material of this disclosure contains a hardening agent. The type of curing agent is not particularly limited and can be selected from those commonly used as underfill materials. One type of curing agent may be used alone, or two or more types may be used in combination. 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.

[0034] There are no particular restrictions on amine-based curing agents. For example, compounds containing two or more amino groups selected from the group consisting of primary and secondary amino groups (hereinafter also simply referred to as "amino groups") in one molecule are preferred, compounds containing two to four amino groups in one molecule are more preferred, and compounds containing two amino groups in one molecule (diamine compounds) are even more preferred.

[0035] From the viewpoint of making the underfill material liquid at room temperature, it is preferable to select a curing agent such that the entire curing agent becomes liquid at room temperature. That is, if only one type of curing agent is included, it is preferable that the curing agent is liquid at room temperature. If there is a combination of two or more types of curing agents, all of the two or more curing agents may be liquid at room temperature, or some of the curing agents may be solid at room temperature, and the combination may become liquid at room temperature when the two or more curing agents are mixed. When using a hardening agent that is solid at room temperature, the content of the solid hardening agent is preferably 20% by mass or less of the total hardening agent, from the viewpoint of fluidity.

[0036] 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, and even more preferably an aromatic amine compound that is liquid at room temperature and has two amino groups in one molecule.

[0037] 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; triethyldiaminobenzenes such as 1,3,5-triethyl-2,6-diaminobenzene; and diaminodiphenylmethanes such as 3,3'-diethyl-4,4'-diaminodiphenylmethane and 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane.

[0038] Among the above compounds, diaminodiphenylmethane and diethyltoluenediamine are preferred from the viewpoint of storage stability. When at least one of diaminodiphenylmethane and diethyltoluenediamine is used as a curing agent, the total content is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to the total curing agent. The upper limit of the above total content is not particularly limited, and for example, it may be 100% by mass or less relative to the total curing agent.

[0039] When using an aromatic amine compound that is liquid at room temperature as a curing agent, from the viewpoint of fully exhibiting its performance, its content is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to the total curing agent. The upper limit of the above content is not particularly limited, and it is sufficient if it is 100% by mass or less relative to the total curing agent.

[0040] When an aromatic amine compound is used 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 even more preferably 30 g / mol to 70 g / mol.

[0041] The active hydrogen equivalent of the curing agent refers to the value calculated based on the amine value measured in accordance with JIS K7237:1995.

[0042] There are no particular restrictions on the equivalent ratio of epoxy resin to curing agent in the underfill material (moles of epoxy groups in the epoxy resin / moles of active hydrogen in the curing agent). From the viewpoint of minimizing the amount of unreacted material, the ratio of moles of epoxy groups in the epoxy resin to moles of active hydrogen in the curing agent is preferably 0.7 to 1.6, more preferably 0.8 to 1.4, and even more preferably 0.9 to 1.2.

[0043] (Inorganic filler) The underfill material of this disclosure contains an inorganic filler. The type of inorganic filler is not particularly limited. Specifically, examples include 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, fossilite, steatite, spinel, mullite, titania, talc, clay, mica, and other inorganic materials. Inorganic fillers with flame retardant properties may also be used. Examples of inorganic fillers with flame retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxides, and zinc borate. Among these, fused silica is preferred from the viewpoint of reducing the coefficient of thermal expansion, and alumina is preferred from the viewpoint of high thermal conductivity. One type of inorganic filler may be used alone, or two or more types may be used in combination. Examples of inorganic fillers in various forms include powder, beads formed from spherical powder, and fibers.

[0044] The content of 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 is preferably 40% to 70% by mass, and more preferably 50% to 65% by mass relative to the total underfill material.

[0045] The inorganic filler may contain silica particles. From the viewpoint of the fluidity and packing properties of the underfill material, the average particle size of the silica particles is preferably 0.2 μm to 5 μm, more preferably 0.2 μm to 3 μm, even more preferably 0.3 μm to 1 μm, and particularly preferably 0.4 μm to 0.8 μm.

[0046] The inorganic filler may contain large-diameter silica particles with a larger average particle diameter and small-diameter silica particles with a smaller average particle diameter. The preferred range for the average particle diameter of the large-diameter silica particles is the same as the preferred range for the average particle diameter of the silica particles described above.

[0047] The average particle size of the small-diameter silica particles is preferably 7 nm to 100 nm, and 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 tends not to increase easily, and deterioration of fluidity is less likely to occur. 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 lower.

[0048] The proportion of silica particles or large-diameter silica particles in the inorganic filler may be 70% by mass or more, or 75% by mass or more. Furthermore, 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.

[0049] The proportion of small-diameter silica particles in the inorganic filler may be 0% by mass, 0.5% or more by mass, or 10% or more by mass. Furthermore, the proportion of small-diameter silica particles in the inorganic filler may be 30% or less by mass, or 25% or less by mass.

[0050] The average particle size of inorganic fillers can be measured by the following method. When measuring inorganic fillers with an average particle diameter of 20 nm or more, the inorganic filler to be measured is added to a solvent (e.g., pure water) along with 1% to 8% by mass of a surfactant in the range of 1% to 5% by mass. The inorganic filler is dispersed by vibrating in a 110W ultrasonic cleaner for 30 seconds to 5 minutes. Approximately 3 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 (LA920, manufactured by Horiba, Ltd.) 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 smaller diameter side in the volume-based particle size distribution reaches 50%. When measuring inorganic fillers with an average particle diameter of less than 20 nm, the inorganic filler may be imaged using an electron microscope or the like, the particle diameter of each individual particle may be measured, and the particle diameter obtained by the arithmetic mean of the particle diameters of 100 arbitrarily selected particles may be used as the average particle diameter of the inorganic filler. If the sample to be measured is a hardened material, for example, the ash content obtained as residue after processing the hardened material at a high temperature of 800°C or higher in a muffle furnace can be measured using the method described above.

[0051] When large-diameter silica particles and small-diameter silica particles are used as inorganic fillers, the ratio of the average particle diameter of the small-diameter silica particles to the average particle diameter of the large-diameter silica particles (average particle diameter of large-diameter silica particles / average particle diameter of small-diameter silica particles) is preferably 7 to 120, more preferably 10 to 110, and even more preferably 20 to 100.

[0052] When large-diameter silica particles are used as an inorganic filler, there are no particular limitations on the method for determining the ratio of small-diameter silica particles to large-diameter silica particles in the inorganic filler. For example, the particle size distribution (frequency distribution) based on volume of the inorganic filler can be determined, the peaks corresponding to small-diameter silica particles and the peaks corresponding to large-diameter silica particles can be separated at the valleys between them, and the ratio of small-diameter silica particles to large-diameter silica particles can be determined by dividing the volume of particles in each separated range by the total volume of the inorganic filler. If the composition of the underfill material is known, the ratio of small-diameter silica particles to large-diameter silica particles in the inorganic filler can be determined from the composition of the underfill material. Note that the calculation method is not limited to the above method.

[0053] (Silicone compounds) The underfill material of this disclosure contains a silicone compound comprising at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound (a 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 a polyester-modified silicone compound may be used alone or two or more types may be used in combination, and one or more polyglycerin-modified silicone compounds and one or more polyester-modified silicone compounds may be combined. In this 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 this disclosure, polyglycerin-modified and polyester-modified silicone compounds are classified as polyglycerin-modified silicone compounds.

[0054] From the viewpoint of effectively suppressing bleed formation, the content of the silicone compound in the underfill material is preferably 0.0001% to 1% by mass relative to the total underfill material. Furthermore, from the viewpoint of the filling speed of the underfill material into the gap between electronic components such as semiconductor elements and the wiring substrate, it is more preferably 0.001% to 0.25% by mass, and even more preferably 0.005% to 0.15% by mass.

[0055] The silicone compound may contain only one of the polyglycerin-modified silicone compound and the polyester-modified silicone compound, or both. It is preferable that the silicone compound contains the polyglycerin-modified silicone compound.

[0056] The polyglycerin-modified silicone compound is not particularly limited as long as it is a silicone compound having multiple structural units derived from glycerin, but it is preferably a silicone compound having multiple structural units derived from glycerin in at least one of the main chain and side chains, and more preferably a polydimethylsiloxane derivative having multiple structural units derived from glycerin in at least one of the main chain and side chains.

[0057] The polyglycerin-modified silicone compound may be an alkyl-modified polydimethylsiloxane derivative or an alkyl-unmodified polydimethylsiloxane derivative. From the viewpoint of suitably suppressing bleed formation, it is preferable that the polyglycerin-modified silicone compound is an alkyl-unmodified polydimethylsiloxane derivative.

[0058] The polyester-modified silicone compound is not particularly limited as long as it is a silicone compound having multiple ester groups (-C(=O)-O-), but it is preferably a silicone compound having multiple ester groups on at least one of the main chain and side chains, and more preferably a polydimethylsiloxane derivative having multiple ester groups on at least one of the main chain and side chains.

[0059] When the silicone compound includes a polyester-modified silicone compound, it is preferable that the polyester-modified silicone compound includes a polyether-polyester-modified silicone compound. Examples of polyether-polyester-modified silicone compounds include silicone compounds having at least one of the main chain and side chains as constituent units derived from an ester group and an alkylene glycol. Examples of alkylene glycols include ethylene glycol, polypropylene glycol, and combinations thereof.

[0060] The polyester-modified silicone compound may be a polydimethylsiloxane derivative that has been modified in a manner other than polyester modification (for example, by ether modification), or it may be a polydimethylsiloxane derivative that has not been modified in a manner other than polyester modification.

[0061] The specific modified silicone compound may be a compound represented by the following general formula (1).

[0062] [ka]

[0063] In general formula (1), R 1 These terms independently represent a hydrocarbon group, an organic group having multiple constituent units derived from glycerol, or an organic group having multiple ester groups. If the compound represented by general formula (1) is a polyglycerol-modified silicone compound, then R 1 At least one of them is an organic group having multiple constituent units derived from glycerol. If the compound represented by general formula (1) is a polyester-modified silicone compound, then R 1 At least one of these is an organic group having multiple ester groups. l is between 0 and 100.

[0064] In general formula (1), R 1 Examples of hydrocarbon groups represented by include 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, it is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Alkyl groups may be linear, cyclic, or branched. Specifically, examples include 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, and cyclohexyl group. Examples of alkenyl groups include vinyl group and allyl group. Among these, from the viewpoint of availability, methyl group or ethyl group is preferred, and methyl group is more preferred. Also, R 1 Some of the alkyl groups are other than methyl groups, and the remaining R 1 It may be a methyl group, and all R 1 It may also be a methyl group.

[0065] The constituent units derived from glycerol may, for example, be those represented by the following formula (2). The polyglycerol-modified silicone compound may have a structure in which multiple constituent units represented by formula (2) are bonded together.

[0066] [ka]

[0067] Specific examples of silicone compounds having multiple constituent units derived from glycerin include compounds containing the structure represented by formula (3) and compounds containing the structure represented by formula (4). In formula (3), n represents a number of 2 or more. [Chemical] [Chemical]

[0068] The weight average molecular weight of the specific modified silicone compound is not particularly limited. From the viewpoint of further suppressing the occurrence of bleed, for example, it is preferably 300 to 10,000, more preferably 500 to 8,000, and even more preferably 1,000 to 6,000. In the present disclosure, the weight average molecular weight is a value determined by conversion using a calibration curve of standard polystyrene using gel permeation chromatography.

[0069] The viscosity of the specific modified silicone compound, preferably the viscosity of the polyglycerol-modified silicone at 25°C, is not particularly limited. For example, it is preferably 500 mm 2 / s to 50,000 mm 2 / s, more preferably 1,000 mm 2 / s to 10,000 mm[[ID=?]] 2 / s, and even more preferably 2,000 mm 2 / s to 5,000 mm 2 / s. [[ID=?]] The viscosity of the specific modified silicone compound means the kinematic viscosity at 25°C. The viscosity in the present disclosure is a value of the kinematic viscosity measured using a capillary viscometer by a method conforming to JIS K7367-1:2002.

[0070] Commercially available products may be used for the specific modified silicone compound. Examples of commercially available 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 Soft Care GS-G, etc. manufactured by Kao Corporation.

[0071] It should be noted that there seems to be an incorrect line number reference in the original text where "[[ID=?]]" is shown. Please check and correct it if possible for a more accurate translation.The silicone compound may or may not contain silicone compounds other than specific modified silicone compounds. Silicone compounds other than specific modified silicone compounds may be unmodified silicone compounds or modified silicone compounds. Examples of modified silicone compounds include polyether-modified silicone compounds, carboxy-modified silicone compounds, and amino-modified silicone compounds.

[0072] The content of a specific modified silicone compound in the silicone compound may be 70% to 100% by mass, 80% to 100% by mass, or 90% to 100% by mass, relative to the total silicone compound.

[0073] (Coupling agent) The underfill material of this disclosure may contain a coupling agent. The coupling agent plays a role in strengthening the adhesion between the resin component in the underfill material and the inorganic filler, or between the resin component and the components of the electronic device. The coupling agent is not particularly limited and can be selected from those commonly used as components of underfill material. Specifically, examples include silane compounds such as aminosilanes, epoxysilanes, mercaptosilanes, alkylsilanes, ureidosilanes, and vinylsilanes having one or more amino groups selected from the group consisting of primary, secondary, and tertiary amino groups, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. Among these, silane compounds are preferred from the viewpoint of filling properties, and epoxysilanes are more preferred.

[0074] If 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 components of the electronic device, as well as improving the filling performance, for example, the content is preferably 0.05% to 10% by mass, more preferably 0.2% to 5% by mass, and even more preferably 0.4% to 1% by mass relative to the total underfill material.

[0075] (Other ingredients) The underfill material may contain, as necessary, other additives in addition to the components mentioned above, such as curing accelerators, ion trapping agents, antioxidants, organic solvents, mold release agents, colorants, rubber particles, leveling agents, and defoaming agents.

[0076] -Curing accelerator- The underfill material of this disclosure may contain a curing accelerator. The type of curing accelerator is not particularly limited, and known curing accelerators can be used. Specifically, cycloamidine compounds such as 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, and 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7; and cycloamidine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, and 2,3-dimethoxy-5-methyl-1,4-benzoquinone. Compounds having intramolecular polarization obtained by adding compounds with π bonds, such as quinone compounds like benzyldimethylamine, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, diazophenylmethane, and phenolic resins; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of tertiary amine compounds; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole Examples include imidazole compounds such as tilimidazole; derivatives of imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; phosphorus compounds having intramolecular polarization obtained by adding compounds having π bonds such as maleic anhydride, the above quinone compounds, diazophenylmethane, and phenolic resins to organic phosphine compounds; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylmorpholine tetraphenylborate; derivatives of tetraphenylboron salts; and adducts of phosphine compounds such as triphenylphosphonium-triphenylborane and N-methylmorpholine tetraphenylphosphonium-tetraphenylborate with tetraphenylboron salts. The curing accelerator may be used alone or in combination of two or more types.

[0077] If the underfill material contains a curing accelerator, the content of the curing accelerator is preferably 0.1% to 8% by mass relative to the total amount of epoxy resin and curing agent.

[0078] -Ion trap agent- The underfill material of the present disclosure may contain an ion trap agent. The ion trap agent that can be used in the present disclosure is not particularly limited as long as it is an ion trap agent generally used in underfill materials for manufacturing electronic component devices. Examples of the ion trap agent include compounds represented by the following general formula (VI-1) or the following general formula (VI-2).

[0079] Mg 1-a Al a (OH)2(CO3) a / 2 ·uH2O (VI-1) (In the general formula (VI-1), a is 0 < a ≤ 0.5, and u is a positive number.) BiO b (OH) c (NO3) d (VI-2) (In the general formula (VI-2), b is 0.9 ≤ b ≤ 1.1, c is 0.6 ≤ c ≤ 0.8, and d is 0.2 ≤ d ≤ 0.4.)

[0080] The ion trap agent is available as a commercial product. Examples of the compound represented by the general formula (VI-1) include, for example, "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd., trade name), which is available as a commercial product. Also, examples of the compound represented by the general formula (VI-2) include, for example, "IXE500" (manufactured by Toagosei Co., Ltd., trade name), which is available as a commercial product.

[0081] In addition, examples of ion trap agents other than those described above include hydrated 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.

[0082] If the underfill material contains an ion trapping agent, the content of the ion trapping agent is preferably 1 part by mass or more per 100 parts by mass of epoxy resin, from the viewpoint of achieving sufficient moisture resistance reliability. From the viewpoint of fully exhibiting the effects of other components, the content of the ion trapping agent is preferably 15 parts by mass or less per 100 parts by mass of epoxy resin, more preferably 1 to 10 parts by mass, and even more preferably 2 to 5 parts by mass.

[0083] Furthermore, the average particle size of the ion trapping agent is preferably 0.1 μm to 3.0 μm, and the maximum particle size is preferably 10 μm or less. The average particle size of the ion trapping agent can be measured in the same manner as for inorganic fillers.

[0084] -Antioxidant- The underfill material of this disclosure may contain an antioxidant. Conventionally known antioxidants can be used. Examples of phenolic antioxidants include compounds having at least one alkyl group at the ortho position of the phenol core, such as 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), and 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 (3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 4,6-bis(dodecylthiomethyl)-o-cresol, bis[3,5-di-t-butyl-4-hydroxybenzyl(ethoxy)phosphinate]calcium, 2,4-bis(octylthiomethyl)-6-methylphenol, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 6-[3-(3-t-butyl-4 -Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosfepine, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 2,2'-methylenebis-(4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-4-ethylphenol, 1,1,Examples include 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, triethylene glycol-bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], tris(3,5-di-t-butyl-4-hydroxybenzyl)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, and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine. Examples of organosulfur compound antioxidants include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythrityltetrakis(3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, and 4,4'-thiobis(6-t-butyl-3-methyl) Examples include methylphenol, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,6-bis(dodecylthiomethyl)-o-cresol, 2,4-bis(octylthiomethyl)-6-methylphenol, and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine. Examples of amine compound-based antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, and 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine. Among amine compound antioxidants, dicyclohexylamine is commercially available, such as D-CHA-T manufactured by Shin-Nippon Rika Co., Ltd., and its derivatives include ammonium dicyclohexylamine nitrite, N,N-di(3-methyl-cyclohexyl)amine, N,N-di(2-methoxy-cyclohexyl)amine, and N,N-di(4-bromo-cyclohexyl)amine. Examples of phosphorus-based antioxidants include trisnonylphenyl phosphite, triphenyl phosphite, 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]dioxaphosfepin-6-yl]oxy]-N,N-bis[2-{[2,4,8, Examples include 10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepine-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]dioxaphosfepine, and diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate. Antioxidants may be used individually or in combination of two or more. Specific examples of antioxidants include compounds containing at least one of the following in the same molecule: a phenolic hydroxyl group, a phosphorus atom, a sulfur atom, or an amine. These compounds may be listed multiple times.

[0085] If the underfill material contains an antioxidant, 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.

[0086] -Organic Solvents- The underfill material of this disclosure may contain organic solvents as needed to reduce viscosity. In particular, when at least one of a solid epoxy resin and a solid curing agent is used, 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 underfill material.

[0087] The content of volatile components, including organic solvents, is not particularly limited as long as it does not form air bubbles when the underfill material hardens. 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 underfill material. The lower limit of the content of volatile components, including organic solvents, is not particularly limited as long as it is 0% by mass or more. In this disclosure, the volatile components of the underfill material are calculated based on the weight difference before and after heating the underfill material at 180°C for 30 minutes.

[0088] -Release agent- The underfill material 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. If the underfill material contains a release agent, the release agent content is preferably 10% by mass or less relative to the total amount of epoxy resin and hardener, and from the viewpoint of exhibiting its effect, it is preferably 0.5% by mass or more.

[0089] -Coloring agent- The underfill material of this disclosure may contain colorants such as dyes and carbon black. The colorants may be used individually or in combination of two or more types.

[0090] 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. If the underfill material 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.

[0091] -Rubber particles- The underfill material 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.

[0092] 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, etc., 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 underfill material low. Silicone rubber particles are commercially available from companies such as Toray Dow Corning Silicone Co., Ltd. and Shin-Etsu Chemical Co., Ltd.

[0093] When the underfill material contains rubber particles, the average particle size of the rubber particles is preferably fine in order to modify the underfill material with high uniformity. 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 underfill material tends to improve further. When the volume 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 underfill material improve, and it tends to be less likely to cause voids and unfilled areas. The average particle size of rubber particles is measured using the same method as for inorganic fillers. If the underfill material contains rubber particles, the rubber particle content is preferably 3% to 30% by mass, more preferably 5% to 28% by mass, and even more preferably 10% to 25% by mass, relative to the total epoxy resin.

[0094] <Uses of underfill material> The underfill material can be applied, for example, to semiconductor devices equipped with electronic components, as described later. Furthermore, in recent years, with the increasing speed of semiconductor devices, low dielectric constant interlayer insulating films are sometimes formed on semiconductor devices. These interlayer insulating films have low mechanical strength and are easily damaged by external stress, making them prone to failure. This tendency becomes more pronounced as the size of the semiconductor device increases, so there is a need to reduce the stress caused by the underfill material. The underfill material of this disclosure provides excellent reliability even for flip-chip connected electronic component devices that incorporate semiconductor elements with a size of 2 mm or more on the longer side and an interlayer insulating film with a dielectric constant of 3.0 or less. Furthermore, it is possible to provide electronic component devices that exhibit good fluidity and filling properties 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 200 μm or less, and that also have excellent reliability in terms of moisture resistance, thermal shock resistance, etc.

[0095] <Method for manufacturing underfill material> Underfill material can be obtained, for example, by stirring, melting, mixing, and dispersing epoxy resin, curing agent, inorganic filler, and specific silicone compounds, as well as other components used as needed, either together or separately, while applying heat treatment as necessary. The equipment for mixing, stirring, and dispersing these components is not particularly limited and includes a mixing machine equipped with a stirring device, heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. Underfill material can be obtained by mixing, kneading, and degassing the above components as needed using this equipment. As silica particles, a mixture of silica particles pre-mixed with epoxy resin may be used to improve particle dispersibility.

[0096] <Electronic Components and Devices> The electronic component apparatus of the present 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 underfill material of the present disclosure disposed in the gap between the substrate and the electronic component. The electronic component apparatus of the present disclosure can be obtained by sealing the electronic component with the underfill material of the present disclosure. Because the electronic component is sealed with the underfill material, the electronic component apparatus of the present disclosure is highly reliable.

[0097] Examples of electronic component devices include those obtained by mounting electronic components such as semiconductor elements, 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 sealing the necessary parts with the underfill material of this disclosure. In particular, electronic component devices in which semiconductor elements are flip-chip bonded by bump connection to wiring formed on rigid circuit boards, flexible circuit boards, or glass are one example of devices to which the underfill material 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).

[0098] The underfill material of this disclosure is useful as an underfill material for flip chips where high reliability is required. The flip chip fields to which the underfill material of this disclosure is particularly suitable include cases where the bump material connecting the wiring substrate and the semiconductor element is not only conventional lead-containing solder, but also lead-free solder such as Sn-Ag-Cu. Even for flip chips with bump connections using lead-free solder, which is physically more brittle than conventional lead solder, the underfill material of this disclosure tends to maintain good reliability. Furthermore, applying the underfill material of this disclosure when mounting chip-scale packages such as wafer-level CSPs (Chip Size Packages) onto a substrate tends to improve reliability.

[0099] <Manufacturing method for electronic component devices> A method for manufacturing an electronic component device according to the present disclosure includes a step of 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 of the present disclosure. There are no particular limitations on the process of sealing a substrate having a circuit layer and an electronic component using the underfill material of this disclosure. For example, there is a post-fill method in which, after connecting the electronic component and the substrate having a circuit layer, the underfill material is applied to the gap between the electronic component and the substrate using capillary action, and then the curing reaction of the underfill material is carried out. There is also a pre-coating method in which the underfill material of this disclosure is applied to at least one surface of the substrate having a circuit layer and the electronic component in advance, and when the electronic component is connected to the substrate by thermal compression bonding, the connection of the electronic component and the substrate and the curing reaction of the underfill material are carried out in a single process. Methods for applying underfill material include casting, dispensing, and printing.

[0100] The curing conditions for the underfill material are not particularly limited, but it is preferable to heat it at 80°C to 165°C for 1 minute to 150 minutes. [Examples]

[0101] The present invention will be described below based on examples, but the present invention is not limited to the following examples.

[0102] [Preparation of underfill material] Each component shown in Tables 1 and 2 was blended in the amounts (parts by mass) shown in Tables 1 and 2, and then kneaded and dispersed using a three-roll mill and a vacuum pulverizer to prepare the underfill materials for the examples and comparative examples. Details of each material shown in Table 1 are as follows. A blank space (-) in Table 1 indicates that the component was not included.

[0103] • Epoxy resin 1: A liquid bifunctional epoxy resin with an epoxy equivalent of 160 g / mol, obtained by epoxidizing bisphenol F. • Epoxy resin 2: A trifunctional liquid epoxy resin with an epoxy equivalent of 95 g / mol, obtained by epoxidizing aminophenol. • Epoxy resin 3: A liquid bifunctional epoxy resin with an epoxy equivalent of 143 g / mol, obtained by epoxidizing naphthalene. • Hardener 1: Diethyltoluenediamine with an active hydrogen equivalent of 45 g / mol • Hardener 2: Diethyldiaminodiphenylmethane with an active hydrogen equivalent of 63 g / mol • 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, polyglycerin denatured) • Silicone compound 2: KF-6104 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25°C: 4,000 mm) 2 ( / s, polyglycerin denatured) • Silicone compound 3: KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25°C: 4,000 mm) 2 ( / s, polyglycerin modification and alkyl modification) • Silicone compound 4: KF-6106 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25°C: 3,500 mm) 2 ( / s, polyglycerin denatured) • Silicone compound 5: BYK-370 (manufactured by BIC Chemie Japan Co., Ltd., kinematic viscosity at 40°C: approximately 1 mm³) 2 (polyester modified) • Silicone compound 6: BYK-375 (manufactured by BIC Chemie Japan Co., Ltd., polyether-polyester modified) • Silicone compound 7: BYK-302 (manufactured by Bic Chemie Japan Co., Ltd., hydroxyl group-free) • Silicone compound 8: BYK-326 (manufactured by Bic Chemie Japan Co., Ltd., hydroxyl group-free) • Silicone compound 9: BYK-333 (manufactured by BIC Chemie Japan Co., Ltd., hydroxyl group-free) • Silicone compound 10: BYK-349 (manufactured by Bic Chemie Japan Co., Ltd., hydroxyl group-free)

[0104] [evaluation] Test electronic component devices were fabricated using the underfill materials prepared in the examples and comparative examples, and bleed and filling speed were evaluated. The results are shown in Tables 1 and 2. The specifications for the test electronic component device are as follows: The test electronic component device was manufactured by applying 20 mg of underfill material to the gap between the substrate and the semiconductor element using a dispensing method under conditions of 110°C, and then sealing the gap by curing it in air at 150°C for 2 hours.

[0105] • Semiconductor element size: 10mm x 10mm x 0.4mm thick • Circuit board size: 35mm x 35mm x 1mm thick • Circuit board (core) type: E-679FG(G) (Manufactured by Showa Denko Materials Co., Ltd., product name) • Solder resist type: SR-7300G (manufactured by Showa Denko Materials Co., Ltd., product name) • Gap between substrate and semiconductor element: 50 μm

[0106] (1) Length of bleed on the circuit board (evaluation of bleed) The area near the fillet contact point on the substrate of the sealed electronic component device was observed using a laser microscope (Digital microscope VHX-500 (product name) manufactured by Keyence Corporation), and the length of the underfill material bleed was measured. A shorter bleed length indicates that the occurrence of bleeding has been suppressed. The bleed length in the Examples and Comparative Examples was determined based on the measurement results of the bleed length in Comparative Example 5. That is, the bleed length (μm) in the Examples or Comparative Examples / the bleed length (μm) in Comparative Example 5 were determined, respectively. The criteria for determining bleed are as follows. -Judgment criteria- A: The bleed (μm) in the example or comparative example / the bleed (μm) in comparative example 5 is less than 1.00. B: The bleed (μm) in the example or comparative example is 1.00. C: The bleed (μm) in the example or comparative example / the bleed (μm) in comparative example 5 is greater than 1.00.

[0107] (2) Flow test (evaluation of filling rate) One mg of underfill material was injected into the gap between the support member (glass substrate) and the cover glass used as a substitute for the electronic component using a dispensing method under conditions of 110°C, and the time (in seconds) until the gap was completely filled with the underfill material was measured. The specifications of the evaluation sample are as follows. Table 2 shows the relative values ​​for each example, with the value in Comparative Example 5 set as the baseline value of 1.0, for the filling speed obtained as described above.

[0108] [Specifications of the evaluation sample] • Glass substrate size: 76mm x 26mm Micro-slide glass (Matsunami Glass Industry Co., Ltd.) (Manufactured by a company) • Cover glass size: 20mm x 20mm (manufactured by Matsunami Glass Industry Co., Ltd.) • Gap between substrate and semiconductor element: 25 μm

[0109] [Table 1]

[0110] [Table 2]

[0111] As shown in Table 1, in Comparative Examples 1-4, which used silicone compounds that do not contain hydroxyl groups (e.g., polyether-modified silicone compounds), the evaluation of bleed was worse than in Comparative Example 5, which did not use a silicone compound. On the other hand, as shown in Tables 1 and 2, in Examples 1 to 11, which used a predetermined amount of a silicone compound containing at least one of a polyglycerin-modified silicone compound and a polyester-modified silicone compound, the bleed evaluation was better than in Comparative Example 5, which did not use a silicone compound.

[0112] The disclosure of Japanese Patent Application No. 2021-081207, filed on 12 May 2021, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. An underfill resin composition comprising 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 polyether-polyester-modified silicone compound, wherein the content of the silicone compound is 0.0001% to 1% by mass relative to the total amount of the underfill resin composition, and the content of the inorganic filler is 65% by mass or less relative to the total amount of the underfill resin composition.

2. The underfill resin composition according to claim 1, comprising a polyglycerin-modified silicone compound.

3. The underfill resin composition according to claim 1 or claim 2, comprising a polyether-polyester modified silicone compound.

4. The underfill resin composition according to any one of claims 1 to 3, wherein the curing agent comprises an amine-based curing agent.

5. 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 underfill resin composition according to any one of claims 1 to 4, disposed in the gap between the substrate and the electronic component, An electronic component device equipped with the following features.

6. A method for manufacturing an electronic component device, comprising the step of sealing a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer using an underfill resin composition according to any one of claims 1 to 4.

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