TW202243913A - Resin composition for underfill, electronic component apparatus and manufacturing method thereof - Google Patents

Abstract

A resin composition for underfill 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.

Description

Resin composition for underfill, electronic component device, and manufacturing method thereof

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

Conventionally, as a sealing material for sealing semiconductor elements such as transistors and integrated circuits (Integrated Circuit, IC), resins have been mainly used in terms of productivity and cost. Among them, epoxy resins are widely used that are excellent in the balance of properties required for sealing materials, such as workability, formability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

In recent years, so-called bare chip mounting, in which a bare chip is directly mounted on a wiring board, has become mainstream along with miniaturization and thinning of electronic component devices in which semiconductor elements are sealed. Examples of the electronic component device obtained by mounting the bare chip include Chip on Board (COB), Chip on Glass (COG), Tape Carrier Package (TCP), and the like. In these electronic component devices, liquid resin compositions are widely used as sealing materials. In addition, semiconductor elements are directly bump-connected on a wiring board (hereinafter, also simply referred to as "substrate") made of ceramics, glass/epoxy resin, glass/imide resin, polyimide film, etc. In conventional electronic component devices (flip chip), a sealing material called an underfill material has been used to fill the gap (gap) between a semiconductor element and a wiring board connected via bumps. The resin composition used as an underfill plays an important role in protecting electronic components from temperature, humidity and external mechanical force.

In recent years, with the development of information technology, the further miniaturization, high volume and multi-functionalization of electronic equipment have continued to progress, and the smaller diameter, narrower pitch and narrower gaps of bumps based on multi-pins have continued to advance. Furthermore, due to miniaturization of electronic equipment, the distance between the connection terminals arranged on the substrate and the semiconductor element has become narrower than before. Therefore, when the resin component bleeds into the substrate (hereinafter also referred to as "bleed") at the fillet of the semiconductor element sealed with the underfill material, the wiring may be contaminated by the bleed.

Here, in order to improve leakage defects, a liquid sealing resin composition comprising an epoxy resin, a liquid aromatic amine, a filler, and a liquid silicone compound having a carboxyl group or an amine group is disclosed (for example, refer to Patent Document 1 ). [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-219575

[Problem to be Solved by the Invention] Regarding the liquid sealing resin composition described in Patent Document 1, it is described that when a silicone compound not containing a carboxyl group or an amino group is used, it is not possible to suppress leakage. Therefore, in addition to the liquid sealing resin composition described in Patent Document 1, a method of suppressing leakage of the resin component is also sought.

An object of the present disclosure is to provide an underfill resin composition capable of suppressing occurrence of leakage, an electronic component device using the underfill resin composition, and a manufacturing method thereof. [Means to solve the problem]

Specific means for achieving the above-mentioned problems are as follows. <1> A resin composition for underfill, including an epoxy resin, a curing agent, an inorganic filler, and a silicone compound including at least one of a polyglycerol-modified silicone compound and a polyester-modified silicone compound. <2> The resin composition for underfill according to <1>, wherein the content of the silicone compound is 0.0001% by mass to 1% by mass based on the total amount of the resin composition for underfill. <3> The underfill resin composition according to <1> or <2>, wherein the silicone compound includes a polyglycerin-modified silicone compound. <4> The underfill resin composition according to any one of <1> to <3>, wherein, when the silicone compound includes a polyester-modified silicone compound, the polyester-modified The modified silicone compound includes polyether-polyester modified silicone compound. <5> The underfill resin composition according to any one of <1> to <4>, wherein the curing agent includes an amine-based curing agent. <6> An electronic component device, including: a substrate having a circuit layer; an electronic component disposed on the substrate and electrically connected to the circuit layer; and The cured product of the underfill resin composition according to any one of <1> to <5> is arranged in a gap between the substrate and the electronic component. <7> A method of manufacturing an electronic component device, comprising the step of disposing a substrate having a circuit layer, and arranging the substrate on the substrate using the resin composition for underfill according to any one of <1> to <5>. The step of sealing the electronic parts on and electrically connected with the circuit layer. [Effect of the invention]

According to the present disclosure, an underfill resin composition capable of suppressing occurrence of leakage, an electronic component device using the underfill resin composition, and a method of manufacturing the same can be provided.

Hereinafter, the form for carrying out this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and do not limit the present invention. In the present disclosure, the term "step" includes a step that is independent from other steps, even if it cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved, the step is also included. In this disclosure, the numerical values described before and after including "-" in the numerical range represented by "-" are used as the minimum value and the maximum value, respectively. In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the numerical range described in other steps. In addition, in the numerical range described in this indication, the upper limit or the lower limit of the numerical range may be replaced with the value shown in an Example. In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the plurality of substances present in the composition. In the present disclosure, a plurality of particles corresponding to each component may be included. When multiple types of particles corresponding to each component exist in the composition, unless otherwise specified, the particle size of each component refers to a value related to a mixture of the plurality of types of particles present in the composition. In this disclosure, the term "layer" or "film" includes not only the case where the layer or film is formed in the entire area but also the case where it is formed in only a part of the area when looking at the area where the layer or film exists.

＜Resin composition for underfill＞ The underfill resin composition disclosed herein 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.

The resin composition for underfill of the present disclosure (hereinafter also referred to as “underfill material”) contains at least one of polyglycerin-modified silicone compound and polyester-modified silicone compound (hereinafter also referred to as “specific underfill material”). Modified silicone compounds") silicone compounds. Thereby, occurrence of leakage can be suppressed. The reason is presumed as follows. When the underfill material is filled in the gap between electronic components such as semiconductor elements and the wiring board, polar groups such as hydroxyl groups and ester groups contained in the specific modified silicone compound are adsorbed on the wiring board. Therefore, the wetting spread of the preceding liquid film can be suppressed, and the occurrence of leakage can be suppressed.

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

In the present disclosure, the viscosity is defined as a value obtained by multiplying a measured value when an EHD-type rotational viscometer is rotated at a predetermined rotation speed for 1 minute at 25° C. by a predetermined conversion factor. The measured value is obtained with respect to a liquid maintained at 25±1° C. using an EHD rotational viscometer equipped with a conical rotor with a cone angle of 3° and a cone radius of 14 mm. The rotational speed and 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 based on the estimated value.

In the measurement of viscosity, when 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 rotational speed is set to 10 revolutions per minute, and the conversion factor is set to 0.5. When the estimated viscosity is 1.25 Pa·s or more and less than 2.5 Pa·s, set the rotational speed to 5 rpm and set the conversion factor to 1. In the case of full 6.25 Pa·s, set the rotational speed to 2.5 revolutions per minute, and set the conversion factor to 2. For 1 revolution per minute, set the conversion factor to 5.

The viscosity of the underfill is not particularly limited. Among them, from the viewpoint of high fluidity, the viscosity of the underfill material at 25° C. is preferably from 0.1 Pa·s to 100.0 Pa·s, more preferably from 0.1 Pa·s to 50.0 Pa·s, and still more preferably from 0.1 Pa·s to 100.0 Pa·s. Pa·s～30.0 Pa·s.

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

In addition, in the underfill material, the thixotropic index [(2.5 rpm Viscosity at )/(viscosity at 10 rpm)] is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. When the thixotropic index is within the above-mentioned range, the fillet forming property is further improved. Furthermore, the viscosity and thixotropic index of the underfill material can be set within a desired range by appropriately selecting the composition of the epoxy resin, the content rate of the inorganic filler, and the like.

The underfill material disclosed herein includes an epoxy resin, a curing agent, an inorganic filler, and a silicone compound containing a specific modified silicone compound, and may also contain other components as necessary.

(epoxy resin) The underfill of the present disclosure contains epoxy resin. The type of epoxy resin is not particularly limited, and it can be selected from materials generally used as an underfill material. One type of epoxy resin may be used alone, or two or more types may be used in combination.

Examples of the epoxy resin include bisphenol novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins, bisphenol A epoxy resins, and bisphenol F epoxy resins. Aromatic glycidol such as epoxy resin, N,N-diglycidylaniline, N,N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine, etc. Amine type epoxy resin, phenol aralkyl type epoxy resin having at least one of phenylene skeleton or biphenyl skeleton, naphthol aromatic resin having at least one of phenylene skeleton or biphenyl skeleton Aralkyl type epoxy resins such as alkyl type epoxy resins, hydroquinone type epoxy resins, biphenyl type epoxy resins, stilbene type epoxy resins, trisphenol methane type epoxy resins, trisphenol propane Type epoxy resin, alkyl modified trisphenol methane type epoxy resin, epoxy resin containing triazine nucleus, dicyclopentadiene modified phenol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin Resins, alicyclic epoxy resins such as vinylcyclohexene dioxide, dicyclopentadiene oxide, alicyclic diepoxy-adipate, alkanediol diglycidyl Ether, poly(alkylene glycol) diglycidyl ether, enediol diglycidyl ether are equal to difunctional aliphatic epoxy compounds with two epoxy groups in the molecule, etc. For example, the epoxy resin may include bisphenol type epoxy resin, aromatic glycidylamine type epoxy resin, and naphthalene type epoxy resin.

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

From the viewpoint of making the underfill material liquid at normal temperature, it is preferable to select the epoxy resin so that the entire epoxy resin becomes liquid at normal temperature. That is, when only one kind of epoxy resin is included, it is preferable that the epoxy resin is liquid at normal temperature. In the case of a combination of two or more epoxy resins, two or more epoxy resins may be liquid at room temperature, or part of them may be solid epoxy resins at room temperature, and two kinds of epoxy resins may be mixed. The above epoxy resins are combinations that become liquid at room temperature. When using a solid epoxy resin at normal temperature as the epoxy resin, from the viewpoint of fluidity, the content of the solid epoxy resin is preferably 20% by mass or less with respect to the entire epoxy resin.

In the case of using two or more epoxy resins, the epoxy resins may be mixed with other components beforehand, or may be mixed with other components without mixing the epoxy resins with each other.

The content of the epoxy resin in the underfill is not particularly limited, but is preferably 5% by mass to 60% by mass, more preferably 5% by mass 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 includes bisphenol epoxy resin and aromatic glycidylamine 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 with respect to the entire epoxy resin. , more preferably at least 30% by mass, more preferably at least 50% by mass, particularly preferably at least 80% by mass. 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 with respect to the entire epoxy resin.

When bisphenol-type epoxy resin and aromatic glycidylamine-type epoxy resin are used together as the epoxy resin, there is no particular mass ratio (bisphenol-type epoxy resin: aromatic glycidylamine-type epoxy resin) limit. From the viewpoint of heat resistance, adhesiveness, and fluidity, bisphenol-type epoxy resin: aromatic glycidylamine-type epoxy resin is preferably 20:80-95:5, more preferably 40:60-90, for example. : 10, and preferably 60: 40 ~ 80: 20.

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

The epoxy equivalent of the epoxy resin was set to a value measured by a method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7236:2009.

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

Here, the amount of hydrolyzable chlorine is based on the following value: Dissolve 1 g of epoxy resin in the sample in 30 mL of dioxane, add 1 mol/L-KOH (potassium hydroxide) methanol solution 5 mL and refluxed for 30 minutes, the value obtained by potentiometric titration.

(hardener) The underfill of the present disclosure contains a curing agent. The type of curing agent is not particularly limited, and may be selected from materials generally used as underfill materials. A hardening agent may be used individually by 1 type, and may use 2 or more types together. Examples of the curing agent include amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and the like. Among these, as a curing agent, an amine-based curing agent is preferable.

The amine-based hardener is not particularly limited. For example, it is preferable to include two or more ones selected from the group consisting of primary amine groups and secondary amine groups (hereinafter, also referred to as "amine groups") in one molecule. ”), more preferably a compound having 2 to 4 amine groups in one molecule, and still more preferably a compound (diamine compound) having 2 amine groups in one molecule.

From the viewpoint of making the underfill liquid at normal temperature, it is preferable to select the curing agent so that the entire curing agent becomes liquid at normal temperature. That is, when only one kind of curing agent is included, it is preferable that the curing agent is liquid at normal temperature. In the case of a combination of two or more curing agents, two or more curing agents may be liquid at room temperature, or a part of the curing agent may be solid at room temperature, and two or more curing agents may be mixed. A combination that becomes liquid at room temperature when dosed. When using a solid curing agent at normal temperature as the curing agent, from the viewpoint of fluidity, the content of the solid curing agent is preferably 20% by mass or less relative to the entire curing agent.

The compound having an amine group is preferably a compound having an aromatic ring (aromatic amine compound), more preferably an aromatic amine compound that is liquid at normal temperature, further preferably liquid at normal temperature and has 2 An aromatic amine compound with an amine group.

Examples of aromatic amine compounds that are liquid at room temperature include: Toluenediamine; 1,3,5-triethyl-2,6-diaminobenzene and other triethyldiaminobenzenes; 3,3'-diethyl-4,4'-diaminodiphenyl diaminodiphenylmethane, 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane, etc.

Among these compounds, from the viewpoint of storage stability, for example, diaminodiphenylmethane and diethyltoluenediamine are preferable. When at least one of diaminodiphenylmethane and diethyltoluenediamine is used as a curing agent, the total content of the curing agent is preferably, for example, 50% by mass or more, more preferably 70% by mass, based on the entire curing agent. % by mass or more, and preferably more than 80% by mass. The upper limit of the total content is not particularly limited, for example, as long as it is 100% by mass or less based on the entire curing agent.

When using an aromatic amine compound that is liquid at room temperature as a curing agent, the content is preferably at least 50% by mass, more preferably 70% by mass, based on the entire curing agent, from the viewpoint of fully exhibiting its performance. % by mass or more, and preferably more than 80% by mass. The upper limit of the content is not particularly limited as long as it is 100% by mass or less based on the entire curing agent.

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

The active hydrogen equivalent of a hardening|curing agent means the value calculated based on the amine value measured based on JISK7237:1995.

The equivalent ratio of the epoxy resin to the hardener in the underfill material (the number of moles of epoxy groups in the epoxy resin/the number of moles of active hydrogen in the hardener) is not particularly limited. The number of moles of epoxy groups in the epoxy resin/the number of moles of active hydrogen in the hardener is, for example, preferably from 0.7 to 1.6, more preferably from 0.8 to 1.4, from the viewpoint of suppressing the respective unreacted components. , and more preferably 0.9 to 1.2.

(inorganic filler) The underfill 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, silicic acid Calcium, calcium carbonate, potassium titanate, silicon carbide, beryllium oxide, zirconia, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, Inorganic materials such as mica. Inorganic fillers having a flame retardant effect can also be used. Examples of the inorganic filler having a flame-retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxides of magnesium and zinc, zinc borate, and the like. Among these, 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 alone or in combination of two or more. As a state of an inorganic filler, powder, the bead which spheroidized the powder, a fiber, etc. are mentioned.

The content of the inorganic filler in the underfill is not particularly limited, but is preferably 40% by mass to 70% by mass relative to the entire underfill from the viewpoint of the thermal expansion coefficient of the cured product and the fluidity of the underfill. %, more preferably 50 mass % to 65 mass %.

The inorganic filler may contain silica particles. From the viewpoint of fluidity and filling properties of the underfill, 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 still more preferably 0.3 μm to 1 μm. Most preferably, it is 0.4 μm to 0.8 μm.

The inorganic filler may also include large-diameter silica particles with a larger average particle diameter and small-diameter silica particles with a smaller average particle diameter. The preferable range of the average particle diameter of the large-diameter silica particles is the same as the preferable range of the average particle diameter of the above-mentioned silica particles.

The average particle diameter of the small-diameter silica particles is preferably from 7 nm to 100 nm, more preferably from 9 nm to 75 nm. When the average particle diameter of the small-diameter silica particles is 7 nm or more, the viscosity of the underfill material tends to be less likely to increase, and the fluidity tends to be less likely to deteriorate. When the average particle diameter 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-diameter silica particles in the inorganic filler may be 70% by mass or more, or may be 75% by mass or more. Also, 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.

The proportion of the 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. In addition, the proportion of 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 diameter of an inorganic filler can be measured by the following method. When measuring an inorganic filler with an average particle diameter of 20 nm or more, add the inorganic filler to be measured to a solvent (for example, pure water) in the range of 1 mass % to 5 mass % and add 1 mass % % to 8% by mass of surfactant, use a 110 W ultrasonic cleaner to vibrate for 30 seconds to 5 minutes to disperse the inorganic filler. About 3 mL of the dispersion liquid was poured into a measurement cell (cell), and the measurement was performed at 25°C. As for the measuring device, the volume-based particle size distribution was measured using a laser diffraction particle size distribution meter (manufactured by Horiba Seisakusho Co., Ltd., LA920). The average particle diameter is obtained as the particle diameter (D50%) when the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution. When measuring an inorganic filler with an average particle diameter of less than 20 nm, the inorganic filler can be imaged using an electron microscope or the like, the particle diameter of each particle can be measured, and the particle size of 100 particles selected arbitrarily The particle diameter obtained by the arithmetic mean of the diameters was set as the average particle diameter of the inorganic filler. When the measurement sample is a cured product, for example, the ash obtained as a residue after the cured product is processed at a high temperature of 800° C. or higher in a muffle furnace or the like can be measured by the above method.

In the case of using large-diameter silica particles and small-diameter silica particles as the inorganic filler, the ratio of the average particle diameter of the small-diameter silica particles to the average particle diameter of the large-diameter silica particles (large diameter 2 The average particle diameter of silica particles/average particle diameter of small-diameter silica particles) is preferably 7-120, more preferably 10-110, and still more preferably 20-100.

In the case of using large-diameter silica particles as the inorganic filler, there is no particular limitation on the method of obtaining the proportion of small-diameter silica particles and large-diameter silica particles in the inorganic filler. For example, the volume-based particle size distribution (frequency distribution) of the inorganic filler can be obtained, and the peaks corresponding to the small-diameter silica particles and the valleys corresponding to the peaks of the large-diameter silica particles can be cut. The ratio of the small-diameter silica particles to the large-diameter silica particles was obtained by dividing the volume of the particles contained in each cut range by the total volume of the inorganic fillers. When the composition of the underfill material is clear, the ratio of the small-diameter silica particles and the large-diameter silica particles in the inorganic filler can be obtained from the composition of the underfill material. In addition, the calculation method is not limited to the above-mentioned method.

(silicone compound) The underfill of the present disclosure includes a silicone compound containing at least one of a polyglycerol modified silicone compound and a polyester modified silicone compound (a specific modified silicone compound). The type of the 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 polyglycerol modified silicone compound or polyester modified silicone compound may be used alone, two or more types may be used in combination, or more than one polyglycerol modified silicone compound and one or more polyester modified silicone compounds may be used. Silicone compound combination. In the present disclosure, the term "silicone compound" refers to a compound having a main chain formed by a siloxane bond. The silicone compound and the specific modified silicone compound are preferably liquid silicone compounds at 25°C. Furthermore, in this disclosure, polyglycerol-modified and polyester-modified silicone compounds are classified as polyglycerol-modified silicone compounds.

From the viewpoint of appropriately suppressing leakage, the content of the silicone compound in the underfill material is preferably 0.0001% by mass to 1% by mass relative to the entire underfill material. From the viewpoint of the filling rate of the gap between the electronic component and the wiring board, etc., it is more preferably from 0.001 mass % to 0.25 mass %, and more preferably from 0.005 mass % to 0.15 mass %.

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 polyglycerol-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 glycerol, but preferably has a plurality of structural units derived from glycerol on at least one of the main chain and side chain. The silicone compound of the structural unit is more preferably a polydimethylsiloxane derivative having a plurality of structural units derived from glycerin on at least one of the main chain and the side chain.

The polyglycerol-modified silicone compound can be an alkyl-modified polydimethylsiloxane derivative, or a non-alkyl-modified polydimethylsiloxane derivative. The polyglycerol-modified silicone compound is preferably a polydimethylsiloxane derivative that has not been modified with an alkyl group, from the viewpoint of suitably suppressing the occurrence of leakage.

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

When the silicone compound includes a polyester modified silicone compound, the polyester modified silicone compound preferably includes a polyether-polyester modified silicone compound. As a polyether-polyester modified silicone compound, the silicone compound which has an ester group and the structural unit derived from an alkanediol in at least one of a main chain and a side chain is mentioned, for example. As alkanediol, ethylene glycol, polypropylene glycol, and these combinations are mentioned, for example.

The polyester-modified silicone compound may be a polydimethylsiloxane derivative modified other than polyester modified (e.g., ether modified), or may not be modified other than polyester modified polydimethylsiloxane derivatives.

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

[chemical 1]

In the general formula (1), R ¹ each independently represent a hydrocarbon group, an organic group having a plurality of structural units derived from glycerin, or an organic group having a plurality of ester groups. When the compound represented by the general formula (1) is a polyglycerol-modified silicone compound, at least one of R ¹ is an organic group having a plurality of structural units derived from glycerin. When the compound represented by the 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 the general formula (1), examples of the hydrocarbon group represented by R ¹ include aliphatic hydrocarbon groups such as alkyl groups and alkenyl groups. The carbon number of the aliphatic hydrocarbon group is not particularly limited, and is, for example, preferably 1-10, more preferably 1-5, and still more preferably 1-3 from the viewpoint of ease of acquisition. The alkyl group may be linear, cyclic, or branched. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, pentyl, hexyl, heptyl, octyl, Cyclohexyl, etc. Examples of the alkenyl group include a vinyl group, an allyl group, and the like. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable from a viewpoint of easy acquisition. In addition, a part of R ¹ may be an alkyl group other than a methyl group, and the remaining R ¹ may be a methyl group, or all of the R ¹ may be a methyl group.

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

[Chem 2]

[化4]

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

[chemical 4]

The weight average molecular weight of the specific modified silicone compound is not particularly limited. From the viewpoint of further suppressing the occurrence of leakage, for example, 300-10000 is preferable, 500-8000 is more preferable, and 1000-6000 is still more preferable. In the present disclosure, the weight average molecular weight is a value determined by using gel permeation chromatography and converting using a calibration curve of standard polystyrene.

The viscosity of a specific modified silicone compound, preferably the viscosity of a polyglycerol modified silicone compound at 25°C is not particularly limited, for example, it is preferably 500 mm ² /s to 50,000 mm ² /s, more preferably 1000 mm ² /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 refers to the dynamic viscosity at 25°C. The viscosity in this disclosure is the value of the dynamic viscosity measured using the capillary viscometer by the method based on JISK7367-1:2002.

A commercial item can be used for the specific modified silicone compound. Examples of commercially available products include trade names KF-6100, KF-6104, KF-6105, and KF-6106 manufactured by Shin-Etsu Chemical Co., Ltd.; manufactured by BYK-Chemie Japan Co., Ltd. The trade names are BYK-370, BYK-375, etc.; the trade names of Kao Co., Ltd. are Sofcare GS-G, etc.

The silicone compound may or may not contain silicone compounds 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. Examples of modified silicone compounds include polyether-modified silicone compounds, carboxyl-modified silicone compounds, and amino-modified silicone compounds.

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 relative to the entire silicone compound. %~100% by mass.

(coupling agent) The underfill of the present disclosure may also contain a coupling agent. The coupling agent plays a role of strengthening the adhesiveness between the resin component in the underfill material, the inorganic filler, or the resin component and the structural member of the electronic component device. The coupling agent is not particularly limited, and can be selected from coupling agents generally used as components of the underfill material. Specifically, examples include: aminosilanes, epoxysilanes, mercaptosilanes, alkylsilanes, and ureidosilanes having one or more selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups. Silane-based compounds such as silane and vinyl silane; titanium-based compounds; aluminum chelates; aluminum/zirconium-based compounds, etc. Among these, from the viewpoint of filling properties, silane-based compounds are preferable, and epoxysilane is more preferable.

When the underfill material contains a coupling agent, its content is not particularly limited. From the viewpoint of bonding the interface between the resin component and the inorganic filler and the interface between the resin component and the structural member of the electronic component device, and from the viewpoint of improving filling properties, for example, with respect to the entire underfill material, preferably 0.05 % by mass to 10% by mass, more preferably 0.2% by mass to 5% by mass, more preferably 0.4% by mass to 1% by mass.

(other ingredients) The underfill material may contain a curing accelerator, an ion scavenger, an antioxidant, an organic solvent, a mold release agent, a colorant, rubber particles, a leveling agent, an antifoaming agent, and the like as other additives other than the above-mentioned components, if necessary.

-hardening accelerator- The underfill of the present disclosure may also contain a hardening accelerator. The type of hardening accelerator is not particularly limited, and known hardening accelerators can be used. Specifically, 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5,6-dibutyl Amino-1,8-diaza-bicyclo[5.4.0]undecene-7 and other cyclic amidine compounds; addition of maleic anhydride, 1,4-benzoquinone, 2,5-toluene to cyclic amidine compounds quinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, quinone compounds such as 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenolic resin and other compounds with π bonds have intramolecular poles Compounds; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of tertiary amine compounds; 2-methyl Imidazole compounds such as imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tri(4-methane phenylphosphine, diphenylphosphine, phenylphosphine and other organic phosphine compounds; organic phosphine compounds are formed by adding maleic anhydride, the quinone compound, diazophenylmethane, phenol resin and other compounds with π bonds Phosphorus compounds with intramolecular polarization; tetraphenylphosphonium tetraphenyl borate, triphenylphosphine tetraphenyl borate, 2-ethyl-4-methylimidazolium tetraphenyl borate, N-methyl Tetraphenylboron salts such as morpholine tetraphenylborate; derivatives of tetraphenylboron salts; triphenylphosphonium-triphenylborane, N-methylmorpholinetetraphenylphosphonium-tetraphenylborate The adducts of phosphine compounds and tetraphenyl boron salts, etc. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.

When the underfill contains a hardening accelerator, the content of the hardening accelerator is preferably 0.1% by mass to 8% by mass relative to the total amount of the epoxy resin and the hardener.

-Ion Scavenger- The underfill of the present disclosure may also contain ion scavengers. The ion scavenger that can be used in the present disclosure is not particularly limited as long as it is an ion scavenger generally used for an underfill material used in the production of an electronic component device. As an ion trapping agent, the compound represented by following general formula (VI-1) or following general formula (VI-2) is mentioned, for example.

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, 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, d is 0.2≦d≦0.4)

The ion trapping agent can be obtained as a commercial item. As a compound represented by general formula (VI-1), "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd., brand name) can be obtained as a commercial item, for example. In addition, as a compound represented by the general formula (VI-2), "IXE500" (manufactured by Toagosei Co., Ltd., brand name) can be obtained as a commercial item, for example.

Moreover, as an ion trapping agent other than the above, the hydroxide etc. containing the element selected from magnesium, aluminum, titanium, zirconium, antimony, etc. are mentioned. One kind of ion trapping agent may be used alone, or two or more kinds may be used in combination.

When the underfill material contains an ion scavenger, the content of the ion scavenger is preferably 1 part by mass or more relative to 100 parts by mass of the epoxy resin from the viewpoint of realizing sufficient moisture resistance reliability. From the viewpoint of fully exerting the effects of other components, the content of the ion-scavenging agent is preferably at most 15 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably 2 parts by mass, relative to 100 parts by mass of the epoxy resin. parts to 5 parts by mass.

In addition, the average particle diameter of the ion trapping agent is preferably 0.1 μm to 3.0 μm, and the maximum particle diameter is preferably 10 μm or less. The average particle diameter of the ion scavenger can be measured similarly to the case of the inorganic filler.

-Antioxidants- The underfill of the present disclosure may also contain antioxidants. As the antioxidant, previously known antioxidants can be used. Regarding the phenolic compound-based antioxidant, compounds having at least one alkyl group at the ortho position of the phenol nucleus include: 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene bis-(4-methyl-6-tert-butylphenol), 3, 9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8 ,10-tetraoxaspiro[5.5]undecane, 4,4'-butylenebis-(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-th Tributyl-3-methylphenol), tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 2,2-thio- Diethylenylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionamide], isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5 -Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,6-bis(dodecylthiomethyl)-o-cresol , bis[3,5-di-tert-butyl-4-hydroxybenzyl(ethoxy)phosphonite] calcium, 2,4-bis(octylthiomethyl)-6-methylphenol, 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 6-[3-(3-tert-butyl-4- Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphoheptane , 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy-3 ,5-di-tertiary pentylphenyl) ethyl]-4,6-di-tertiary pentylphenyl acrylate, 2,2'-methylenebis-(4-ethyl-6-th Tributylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butyl alkane, triethylene glycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], tris(3,5-di-tert-butyl-4- Hydroxybenzyl) isocyanurate, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 2,5,7, 8-Tetramethyl-2-(4',8',12'-trimethyltridecyl)chroman-6-ol, 2,4-bis-(n-octylthio)-6-( 4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, etc. Examples of organosulfur compound-based antioxidants include: dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3 ,3'-thiodipropionate, pentaerythritol tetrakis(3-lauryl thiopropionate), di-tridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole , 4,4'-thiobis(6-tert-butyl-3-methylphenol), 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl -4-hydroxyphenyl)propionate], 4,6-bis(dodecylthiomethyl)-o-cresol, 2,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine and the like. Examples of amine compound-based antioxidants include N,N'-diallyl-p-phenylenediamine, N,N'-di-second-butyl-p-phenylenediamine, octylated diphenylamine, 2, 4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine and the like. Among the amine compound-based antioxidants, dicyclohexylamine is commercially available under the trade name D-CHA-T manufactured by Nippon Chemical Co., Ltd., and examples of derivatives thereof include dicyclohexyl nitrite Ammonium hexylamine, N,N-bis(3-methyl-cyclohexyl)amine, N,N-bis(2-methoxy-cyclohexyl)amine, N,N-bis(4-bromo-cyclohexyl) Amines etc. Examples of phosphorus compound-based antioxidants include: trinonylphenyl phosphite, triphenyl phosphite, bis[3,5-di-tert-butyl-4-hydroxybenzyl(ethoxy)phosphonous acid Esters] calcium, tris(2,4-di-tert-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis(1,1-dimethyl ether) dibenzo[d ,f][1,3,2]dioxaphosphorin-6-yl]oxy]-N,N-bis[2-{[2,4,8,10-tetrakis(1,1- Dimethylethyl) dibenzo[d,f][1,3,2]dioxaphosphorin-6-yl]oxy}-ethyl]ethylamine, 6-[3-(3 -tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2 ] dioxaphosphorane, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, etc. One type of antioxidant may be used alone, or two or more types may be used in combination. In addition, as specific examples of antioxidants, there are compounds containing a phenolic hydroxyl group and at least one of a phosphorus atom, a sulfur atom, and an amine in the same molecule, and these compounds may be repeatedly listed.

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

-Organic solvents- In the underfill material of the present disclosure, an organic solvent may be blended as necessary for lowering the viscosity. In particular, when using at least one of a solid epoxy resin and a solid hardener, it is preferable to mix an organic solvent in order to obtain a liquid resin composition. The organic solvent is not particularly limited, and examples include: alcohol-based solvents such as methanol, ethanol, propanol, and butanol; ketone-based solvents such as acetone and methyl ethyl ketone; Glycol ether solvents such as butyl glycol ether, propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate; γ-butyrolactone, δ-valerolactone, ε-caprolactone and other lactones amide-based solvents such as dimethylacetamide and dimethylformamide; aromatic-based solvents such as toluene and xylene, etc., can be used alone or in combination of two or more. Among them, an organic solvent having a boiling point of 170° C. or higher is preferable from the viewpoint of avoiding formation of air bubbles due to rapid volatilization when the underfill material is hardened.

The content of volatile components including organic solvents and the like is not particularly limited as long as the underfill does not form bubbles when the underfill is hardened, but it is preferably 5% by mass or less, more preferably 1% by mass of the underfill as a whole. % or less, more preferably 0.1 mass % or less. The lower limit of the content rate of the volatile components including an organic solvent etc. is not specifically limited as long as it is 0 mass % or more. In this disclosure, regarding the volatile component of the underfill, the underfill was heated at 180° C. for 30 minutes, and calculated based on the weight difference before and after heating.

-Release agent- The underfill of the present disclosure may also contain a release agent. The type of release agent is not particularly limited, and known release agents can be used. Specifically, examples thereof include higher fatty acids, carnauba wax, and polyethylene-based waxes. One type of release agent may be used alone, or two or more types may be used in combination. When the underfill contains a mold release agent, the content of the mold release agent is preferably 10% by mass or less relative to the total amount of the epoxy resin and the hardener, and from the viewpoint of exerting its effect, it is preferably 0.5% by mass or more.

-Colorant- The underfill material disclosed herein may also contain colorants such as dyes and carbon black. A coloring agent may be used individually by 1 type, and may use 2 or more types together.

When using electroconductive particles, such as carbon black, as a coloring agent, it is preferable that the content rate of the electroconductive particle is 1 mass % or less of the particle diameter 10 micrometers or more. When the underfill contains conductive particles, the content of the conductive particles is preferably 3% by mass or less, more preferably 0.01% by mass to 1% by mass, based on the total amount of the epoxy resin and the curing agent.

-rubber particles- From the viewpoint of reducing thermal expansion of the cured product, the underfill may contain rubber particles. Rubber particles may be used alone or in combination of two or more. Examples of suitable rubber particles include: styrene-butadiene rubber (styrene-butadiene rubber, SBR), nitrile-butadiene rubber (nitrole-butadiene rubber, NBR), butadiene rubber (butadiene rubber, BR), urethane rubber (urethane rubber, UR), acrylic rubber (acrylic rubber, AR) and other rubber particles. Among them, from the viewpoint of heat resistance and moisture resistance, rubber particles made of acrylic rubber are preferred, and core-shell type acrylic rubber particles are more preferred.

Moreover, silicone rubber particles are mentioned as another example of suitable rubber particle. Examples of silicone rubber particles include silicone rubber obtained by cross-linking linear polyorganosiloxanes such as polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. Ketone rubber particles; silicone rubber particles obtained by coating the surface of the silicone rubber particles with a silicone resin; a core consisting of a core of solid silicone particles obtained by emulsion polymerization or the like and a shell of an organic polymer such as acrylic resin - Shell polymer particles, etc. The shape of these silicone rubber particles may be amorphous or spherical. In order to suppress the viscosity of the underfill to be low, it is preferable to use spherical silicone rubber particles. As for the silicone rubber particles, commercially available products can be obtained from Toray Dow Corning Silicone Co., Ltd., Shin-Etsu Chemical Co., Ltd., and the like.

When the underfill material contains rubber particles, in order to modify the underfill material with high uniformity, the average particle diameter of the rubber particles is preferably fine. The average particle diameter of the rubber particles is preferably in the range of 0.05 μm to 10 μm, more preferably in the range of 0.1 μm to 5 μm. When the average particle diameter of the rubber particles is 0.05 μm or more, the dispersibility to the underfill tends to be further improved. When the average particle diameter of the rubber particles is 10 μm or less, the stress reduction improvement effect tends to be further improved, and the penetration and fluidity of the underfill material into fine gaps are improved, and voids and unfilled tend to be less likely to be caused. The average particle diameter of the rubber particles can be measured by the same method as that of the inorganic filler. When the underfill material contains rubber particles, the content of the rubber particles is preferably 3% by mass to 30% by mass, more preferably 5% by mass to 28% by mass, and still more preferably 10% by mass relative to the entire epoxy resin. % to 25% by mass.

＜Use of underfill material＞ The underfill material can be applied to, for example, a semiconductor device on which electronic components described later are mounted. In addition, in recent years, along with the increase in speed of semiconductor elements, an interlayer insulating film with a low dielectric constant is sometimes formed on the semiconductor elements. The mechanical strength of this interlayer insulating film is weak, and it is easily broken by external stress, so failures are likely to occur. Since this tendency becomes more prominent as the semiconductor element becomes larger, it is required to reduce the stress generated by the underfill material. According to the underfill material of the present disclosure, it is possible to provide excellent reliability even to a flip-chip connection type electronic component device that mounts a semiconductor element whose size is measured on a relatively long side An interlayer insulating film having a thickness of 2 mm or more and a dielectric constant of 3.0 or less. In addition, it is possible to provide a flip-chip connection with a distance of 200 μm or less between the wiring board constituting the electronic component and the bump connection surface of the semiconductor element, which also exhibits good fluidity and filling properties, and has moisture resistance and thermal shock resistance. Electronic parts and devices that are also excellent in reliability.

＜How to make the underfill material＞ The underfill material can be obtained, for example, by adding an epoxy resin, a hardener, an inorganic filler, a specific modified silicone compound, and optionally other components together or separately, and applying heat treatment as necessary. , while stirring, melting, mixing, dispersing, etc. The device for mixing, stirring, and dispersing these components is not particularly limited, and includes a crushing machine including a stirring device, a heating device, etc., a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. mill etc. The underfill material can be obtained by mixing and kneading the above-mentioned components using these devices, and performing defoaming if necessary. As the silica particles, in order to improve the dispersibility of the particles, a mixture obtained by pre-mixing the silica particles with the epoxy resin can also be used.

＜Electronic Components＞ The electronic component device of the present disclosure includes: a substrate having a circuit layer; an electronic component disposed on the substrate and electrically connected to the circuit layer; and a hardened underfill material of the present disclosure disposed on the substrate and the circuit layer. clearance of the electronic parts. The electronic component device of the present disclosure can be obtained by sealing the electronic component with the underfill material of the present disclosure. The electronic component device of the present disclosure is excellent in reliability because the electronic component is sealed by the underfill material.

Examples of electronic components include mounting semiconductor elements, transistors, and diodes on substrates with circuit layers such as lead frames, wired tape carriers, rigid wiring boards, flexible wiring boards, glass, and silicon wafers. Active components such as thyristors, electronic components such as capacitors, resistors, resistor arrays, coils, switches and other passive components, and electronic component devices obtained by sealing required parts with the underfill material of the present disclosure. In particular, as one of the underfill materials applicable to the present disclosure, flip-chip bonding of a semiconductor element and wiring formed on a rigid wiring board, a flexible wiring board, or glass by bump connection is exemplified. electronic parts device. Specific examples include electronic component devices such as flip chip ball grid array (BGA), land grid array (LGA), and chip on film (COF).

The underfill material of the present disclosure is useful as an underfill material for flip chips requiring high reliability. As the flip-chip field to which the underfill material of the present disclosure can be particularly suitably applied, not only the case where the material of the bumps connecting the wiring board and the semiconductor element is conventional lead-containing solder, but also Sn-Ag - In the case of lead-free solders such as Cu-based solders. The underfill material of the present disclosure tends to maintain good reliability even for flip-chip bump connections using lead-free solder that is physically brittle compared to conventional lead solder. In addition, there is a tendency that reliability can be improved by also applying the underfill material of the present disclosure when a chip-level package such as a wafer-level chip size package (CSP) is mounted on a substrate.

<Manufacturing method of electronic component device> The manufacturing method of the electronic component device of the present disclosure has the following steps: using the underfill material of the present disclosure to seal a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer. There is no particular limitation on the step of sealing the substrate having the circuit layer and the electronic component using the underfill material of the present disclosure. For example, it can be mentioned: after the electronic component is connected to the substrate with the circuit layer, the underfill material is applied to the gap between the electronic component and the substrate by capillary phenomenon, and then the hardening reaction of the underfill material is carried out; In the coating method, 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, and when the electronic component is connected to the substrate by thermocompression bonding, the electronic component and the substrate are connected together Reacts with hardening of the underfill. As a method of providing an underfill, a casting method, a dispensing method, a printing method, etc. are mentioned.

The curing conditions of the underfill material are not particularly limited, for example, it is preferably heated at 80° C. to 165° C. for 1 minute to 150 minutes. [Example]

Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to a following Example.

[Preparation of underfill material] Each component shown in Table 1 and Table 2 is allocated with the amount (parts by mass) shown in Table 1 and Table 2, and is mixed and dispersed using a three-roller and a vacuum crushing machine, thereby preparing the compounds of the Examples and Comparative Examples. Underfill. The details of each material shown in Table 1 are as follows. Empty columns (-) in Table 1 indicate no formulation.

・Epoxy resin 1: Liquid bifunctional epoxy resin with an epoxy equivalent of 160 g/mol obtained by epoxidizing bisphenol F ・Epoxy resin 2: Epoxy equivalent of 95 g obtained by epoxidizing aminophenol Trifunctional liquid epoxy resin/mol Epoxy resin 3: Liquid bifunctional epoxy resin with an epoxy equivalent of 143 g/mol obtained by epoxidizing naphthalene Hardener 1: Active hydrogen equivalent 45 g/mol Diethyltoluenediamine 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 Colorant : 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 (Shin-Etsu Chemical Industrial Co., Ltd., viscosity at 25°C: 40,000 mm ² /s, modified with polyglycerin) Silicone compound 3: KF-6105 (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity at 25°C: 40,000 mm ² /s, polyglycerol 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, polyglycerol modified) Silicone Ketone compound 5: BYK-370 (manufactured by BYK-Chemie Japan Co., Ltd., dynamic viscosity at 40°C: about 1 mm ² /s, polyester modified) 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., Hydroxyl free) Silicone compound 8: BYK-326 (manufactured by BYK-Chemie Japan Co., Ltd., free of hydroxyl) Silicone compound 9: BYK-333 (BYK-Chemie Japan Chemie Japan Co., Ltd., hydroxyl-free) Silicone compound 10: BYK-349 (BYK-Chemie Japan Co., Ltd., hydroxyl-free)

[Evaluation] Using the underfill materials prepared in Examples and Comparative Examples, test electronic component devices were produced, and evaluations of leakage and filling speed were performed. The results are shown in Table 1 and Table 2. The specifications of the electronic component device used for the test are as follows. The electronic component device for the test was manufactured as follows: 20 mg of underfill material was applied to the gap between the substrate and the semiconductor element by dispensing at 110°C, and cured at 150°C in air 2 hours, whereby the gap is sealed.

・Size of semiconductor element: 10 mm x 10 mm x 0.4 mm thick · Substrate size: 35 mm x 35 mm x 1 mm thick ・Type of substrate (core): E-679FG (G) (manufactured by Showa Denko Materials Co., Ltd., trade 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) Length of bleeding (leakage) on the substrate (evaluation of leakage) A laser microscope (manufactured by KEYENCE Co., Ltd., digital microscope (Digital microscope) VHX-500 (trade name)) was used to examine the vicinity of the portion of the sealed electronic component device that is in contact with the fillet. Observe and measure the length of seepage (leakage) of the underfill. The shorter the length of bleed (bleed, bleed), it can be judged that the occurrence of bleed is suppressed more. Based on the measurement results of the length of the leak in Comparative Example 5, the length of the leak in the examples and the comparative examples was determined. That is, the leakage (μm) in the example or the comparative example/the leakage (μm) in the comparative example 5 were calculated|required, respectively. Judgment criteria for leakage are as follows. - Judgment criteria - A: The leakage (μm) in Example or Comparative Example/the leakage (μm) in Comparative Example 5 is less than 1.00. B: The leakage (μm) in Example or Comparative Example/the leakage (μm) in Comparative Example 5 is 1.00. C: Leakage (µm) in Example or Comparative Example/Leakage (µm) in Comparative Example 5 is greater than 1.00.

(2) Flow test (evaluation of filling speed) Under the condition of 110°C, inject 1 mg of the underfill material into the gap between the support member (glass substrate) and the cover glass used as a substitute for electronic parts by dispensing, and measure until the gap is completely filled with the underfill material. Time in seconds until filled. The specifications of the samples for evaluation are as follows. Table 2 shows the relative values in each example when the value in Comparative Example 5 is a reference value of 1.0 with respect to the filling speed obtained in this manner.

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

[Table 1] Classification unit Example comparative example 1 2 3 4 5 6 1 2 3 4 5 composition epoxy resin 1 parts by mass 60 60 60 60 60 60 60 60 60 60 60 Epoxy 2 parts by mass 20 20 20 20 20 20 20 20 20 20 20 Epoxy 3 parts by mass 20 20 20 20 20 20 20 20 20 20 20 Hardener 1 parts by mass 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 9.8 Hardener 2 parts by mass 32 32 32 32 32 32 32 32 32 32 32 Inorganic filler parts by mass 213 213 213 213 213 213 213 213 213 213 213 Colorant parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Silicone compound 1 parts by mass 0.36 - - - - - - - - - - Silicone compound 2 parts by mass - 0.36 - - - - - - - - - Silicone compound 3 parts by mass - - 0.36 - - - - - - - - Silicone compound 4 parts by mass - - - 0.36 - - - - - - - Silicone compound 5 parts by mass - - - - 0.36 - - - - - - Silicone compound 6 parts by mass - - - - - 0.36 - - - - - Silicone compound 7 parts by mass - - - - - - 0.36 - - - - Silicone compound 8 parts by mass - - - - - - - 0.36 - - - Silicone compound 9 parts by mass - - - - - - - - 0.36 - - Silicone compound 10 parts by mass - - - - - - - - - 0.36 - Content rate of silicone compound quality% 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0 Evaluation Compared to the length of the bleed (Bleed) of Comparative Example 5 μm/μm 0.63 0.71 0.90 0.81 0.93 0.72 1.12 1.01 1.08 1.02 1.00 Bleed suppression effect - A A A A A A C C C C B

[Table 2] Classification unit Example comparative example 7 8 9 10 11 5 composition epoxy resin 1 parts by mass 60 60 60 60 60 60 Epoxy 2 parts by mass 20 20 20 20 20 20 Epoxy 3 parts by mass 20 20 20 20 20 20 Hardener 1 parts by mass 9.8 9.8 9.8 9.8 9.8 9.8 Hardener 2 parts by mass 32 32 32 32 32 32 Inorganic filler parts by mass 213 213 213 213 213 213 Colorant parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 Silicone compound 1 parts by mass 0.036 0.18 0.36 0.71 1.8 - Content rate of silicone compound quality% 0.01 0.05 0.1 0.2 0.5 0 Evaluation Compared to the length of the bleed (Bleed) of Comparative Example 5 μm/μm 0.89 0.48 0.38 0.38 0.32 1.00 Flow Test (Fill Speed) to Ref 1.0 1.1 1.1 1.4 1.6 1.0

As shown in Table 1, in Comparative Example 1 to Comparative Example 4 using a silicone compound not containing a hydroxyl group (for example, a polyether-modified silicone compound), compared with Comparative Example 5 in which no silicone compound was used, the penetration Leaked ratings worsen. On the other hand, as shown in Table 1 and Table 2, in Examples 1 to 11 using a predetermined amount of a silicone compound containing at least one of a polyglycerol-modified silicone compound and a polyester-modified silicone compound, Among them, the evaluation of leakage was better than that of Comparative Example 5 in which no silicone compound was used.

The entire disclosure of Japanese Patent Application No. 2021-081207 for which it applied on May 12, 2021 is incorporated in this specification by reference. All documents, patent applications, and technical specifications described in this specification are incorporated by reference to the same extent as if each document, patent application, and technical specification were specifically and individually stated to be incorporated by reference. in this manual.

none

none

Claims (7)

A resin composition for bottom filling, including epoxy resin, curing agent, inorganic filler, and silicone compound containing at least one of polyglycerol modified silicone compound and polyester modified silicone compound. The resin composition for underfill according to claim 1, wherein the content of the silicone compound is 0.0001% by mass to 1% by mass relative to the total amount of the resin composition for underfill. The resin composition for underfill according to Claim 1 or Claim 2, wherein the silicone compound includes a polyglycerol-modified silicone compound. The underfill resin composition according to any one of claim 1 to claim 3, wherein, when the silicone compound includes a polyester-modified silicone compound, the polyester-modified silicone The compound comprises a polyether-polyester modified silicone compound. The underfill resin composition according to any one of claims 1 to 4, wherein the curing agent includes an amine-based curing agent. An electronic component device, comprising: a substrate having a circuit layer; an electronic component disposed on the substrate and electrically connected to the circuit layer; and The cured product of the resin composition for underfill according to any one of claims 1 to 5 is arranged in a gap between the substrate and the electronic component. A method of manufacturing an electronic component device, comprising the steps of: using the resin composition for underfill according to any one of claim 1 to claim 5, disposing a substrate having a circuit layer on the substrate, and A step of sealing the electronic components electrically connected to the circuit layer.