TWI811215B - Sealing resin composition, electronic component apparatus and manufacturing method for electronic component apparatus - Google Patents

Abstract

A sealing resin composition contains (A) an epoxy resin, (B) a curing agent containing at least one amino group in one molecule and (C) an inorganic filler, wherein, (C) the inorganic filler contains (C1) a first inorganic filler having an average particle diameter of from 0.1 μm to 20 μm and (C2) a second inorganic filler having an average particle diameter of from 10 nm to 80 nm, and a value obtained by multiplying a specific surface area of (C) the inorganic filler by a ratio that a mass of (C) the inorganic filler occupies in a solid content of the sealing resin composition is 4.0 m² /g or more.

Description

Sealing resin composition, electronic component device, and method for manufacturing electronic component device

The present invention relates to a sealing resin composition, an electronic component device, and a manufacturing method of the electronic component device.

In recent years, in order to cope with the further increase in density of wiring in electronic equipment, flip-chip bonding has been used as a mounting method for semiconductor wafers using system-in-package. The package obtained by flip chip bonding is called a flip chip package (FC-PKG). Generally speaking, in FC-PKG, a liquid resin composition called an underfill is used to seal the gap between the semiconductor chip and the substrate.

In recent years, the demand for FC-PKG for mobile phones has increased, especially the use of small flip-chip chip size package (FC-CSP) semiconductor modules. Currently, the size of the PKG of FC-CSP is about 20 mm or less × 20 mm or less × 2 mm, and further miniaturization is required.

Here, one of the problems associated with the semiconductor underfill material that seals the gap between the semiconductor wafer and the substrate is bleeding. Bleeding in FC-PKG refers to a phenomenon in which a liquid component in a sealing material for semiconductors, which is a liquid resin composition, spreads and bleeds out on the surface of a solder resist applied to a substrate under a semiconductor wafer. If leakage occurs, it may contaminate the connection circuit near where the FC-PKG is installed.

Therefore, in recent years, various studies have been conducted in order to prevent bleeding on the surface of the solder resist. In order to solve the problem of bleeding, a liquid sealing resin composition containing an acrylic-siloxane copolymer (for example, see Patent Document 1) and a liquid sealing resin composition containing an amine group-containing silicone oil (for example, see Patent Document 2) have been reported ) and a liquid sealing resin composition containing a liquid silicone compound having a polyether group and a liquid silicone compound having an amine group (for example, see Patent Document 3). [Prior Art Documents] [Patent Documents]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-6618 [Patent Document 2] Japanese Patent Laid-Open No. 2010-192525 [Patent Document 3] Japanese Patent Laid-Open No. 2012-107149

[Problems to be Solved by the Invention] However, there is a concern that the surface tension of the liquid resin composition may be reduced by adding a siloxane copolymer or a silicone compound. When a liquid resin composition is used as an underfill material, a decrease in the surface tension of the liquid resin composition may lead to a deterioration in the injectability of the package. Therefore, there is a demand for a material that can suppress bleeding independently of a siloxane copolymer or a silicone compound.

The present invention was made in view of the above-mentioned facts, and an object thereof is to provide a sealing resin composition capable of suppressing leakage, an electronic component device using the same, and a manufacturing method of the electronic component device. [Means to solve the problem]

Specific means for solving the above problems are as follows. <1> A sealing resin composition containing (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler It includes (C1) a first inorganic filler with an average particle diameter of 0.1 μm to 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm to 80 nm, and the (C) inorganic filler has a mass of The ratio of the mass of the solid content multiplied by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more. <2> The sealing resin composition according to <1>, wherein the viscosity at 110°C is 0.20 Pa·s or less. <3> The sealing resin composition according to <1> or <2>, wherein the (C2) second inorganic filler with an average particle diameter of 10 nm to 80 nm is added to the (C) inorganic filler The proportion of the material is more than 0.3% by mass. <4> The sealing resin composition according to any one of <1> to <3>, wherein the (C2) second inorganic filler with an average particle diameter of 10 nm to 80 nm is in the (C2) C) The proportion of inorganic fillers is 30% by mass or less. <5> The sealing resin composition according to <1> or <2>, wherein the (C2) second inorganic filler with an average particle diameter of 10 nm to 80 nm is added to the (C) inorganic filler The proportion of the material is 10 mass% to 30 mass%. <6> The sealing resin composition according to any one of <1> to <5>, wherein the first inorganic filler with an average particle diameter of (C1) is 0.1 μm to 20 μm in the (C1) C) The proportion of inorganic fillers is more than 70% by mass. <7> The sealing resin composition according to any one of <1> to <6>, which has a viscosity at 25°C of 0.1 Pa·s to 50.0 Pa·s. <8> The sealing resin composition according to any one of <1> to <7>, wherein the first inorganic filler (C1) with an average particle diameter of 0.1 μm to 20 μm contains silica . <9> The sealing resin composition according to any one of <1> to <8>, wherein the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm contains silica . <10> The sealing resin composition according to any one of <1> to <9>, wherein the content rate of the (C) inorganic filler is 40% by mass to 85% by mass. <11> The sealing resin composition according to any one of <1> to <10>, wherein the (C1) first inorganic filler with an average particle diameter of 0.1 μm to 20 μm has a specific surface area of 1 m ² /g～30 m ² /g. <12> The sealing resin composition according to any one of <1> to <11>, wherein the (C2) second inorganic filler with an average particle diameter of 10 nm to 80 nm has a specific surface area of 20 m ² /g～500 m ² /g. <13> The sealing resin composition according to any one of <1> to <12>, wherein the thixotropic index at 25°C is 0.5 to 1.5. <14> The sealing resin composition according to any one of <1> to <13>, wherein the (B) hardener having at least one amine group in one molecule contains an aromatic amine. <15> The sealing resin composition according to <14>, wherein the aromatic amine has an amine group directly bonded to an aromatic ring and contains one or two of the aromatic rings in one molecule. <16> The sealing resin composition according to any one of <1> to <15>, wherein the (C1) average particle diameter is an average particle diameter of the first inorganic filler of 0.1 μm to 20 μm. The ratio (C1/C2) of the average particle diameter of the second inorganic filler with the average particle diameter of (C2) being 10 nm to 80 nm is 10 to 50. <17> 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 any one of <1> to <16> The cured product of the sealing resin composition is disposed in a gap between the substrate and the electronic component. <18> A method of manufacturing an electronic component device, which includes arranging a substrate having a circuit layer on the substrate using the sealing resin composition according to any one of <1> to <16>, and disposing the substrate with the sealing resin composition. Describes the steps for sealing electronic components that are electrically connected to the circuit layer. [Effects of the invention]

According to the present invention, it is possible to provide a sealing resin composition capable of suppressing bleeding, an electronic component device using the same, and a method of manufacturing an electronic component device.

Hereinafter, the form for carrying out the present invention will be described 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 expressly stated. The same applies to numerical values and their ranges, which do not limit the present invention. In this specification, the term "step" includes steps other than steps that are independent of other steps, even if they cannot be clearly distinguished from other steps, if the purpose of the step is achieved. In this specification, the numerical range expressed using "～" includes the numerical values described before and after "～" as the minimum value and the maximum value respectively. Among the numerical ranges described in stages in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical range described in this specification, the upper limit value or the lower limit value of this numerical range may be replaced with the value shown in an Example. In this specification, when there are multiple substances corresponding to each component in the composition, the content rate of each component in the composition refers to the total content of the multiple substances present in the composition unless otherwise specified. Rate. In this specification, the particle size of each component in the composition, when there are multiple types of particles corresponding to each component in the composition, refers to the mixture of the multiple types of particles present in the composition unless otherwise specified. value. In this specification, the term “layer” includes a case where the layer is formed in the entire region, and also includes a case where the layer is formed in only a part of the region.

<Sealing resin composition> The sealing resin composition of the present disclosure contains (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) inorganic filler, (C) inorganic The filler includes (C1) a first inorganic filler with an average particle diameter of 0.1 μm to 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm to 80 nm. The mass of the (C) inorganic filler is The value obtained by multiplying the proportion to the mass of the solid content by the specific surface area of (C) the inorganic filler is set to 4.0 m ² /g or more.

Hereinafter, the details of each component constituting the sealing resin composition will be described.

-Epoxy resin- The epoxy resin of component (A) imparts curability and adhesiveness to the sealing resin composition, and imparts heat resistance and durability to the cured product of the sealing resin composition. The epoxy resin is preferably a liquid epoxy resin. In this disclosure, a solid epoxy resin may be used together with a liquid epoxy resin as long as it is within a range that can suppress bleeding.

In addition, the so-called liquid epoxy resin refers to an epoxy resin that is liquid at normal temperature (25°C). Specifically, it means that the viscosity measured with an E-type viscometer at 25°C is 1000 Pa·s or less. Regarding the viscosity, specifically, an E-type viscometer EHD type (cone angle 3°, cone diameter 28 mm) was used at a measurement temperature of 25°C and a sample volume of 0.7 ml, with the following as a reference. After setting the rotation speed based on the assumed viscosity of the sample, the value 1 minute after the start of the measurement is set as the measured value. (1) When the assumed viscosity is 100 Pa·s to 1000 Pa·s: the rotation speed is 0.5 rpm (2) When the assumed viscosity is less than 100 Pa·s: the rotation speed is 5 rpm. In addition, the so-called solid Epoxy resin refers to epoxy resin that is solid at room temperature (25°C).

The type of epoxy resin is not particularly limited. Examples of epoxy resins include naphthalene-type epoxy resins; diglycidyl ether-type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; and o-cresol novolac varnishes. Type epoxy resin is represented by the epoxidation of novolac resins of phenols and aldehydes; glycidyl ester type obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin Epoxy resin; glycidylamine type epoxy resin obtained by the reaction of amine compounds such as diaminodiphenylmethane and isocycyanuric acid with epichlorohydrin, etc.

From the viewpoint of viscosity adjustment, the epoxy equivalent of the epoxy resin is preferably 80 g/eq to 250 g/eq, more preferably 85 g/eq to 240 g/eq, and still more preferably 90 g/eq to 230 g/eq. The epoxy equivalent of the epoxy resin is measured by dissolving the weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and tetraethylammonium bromide acetic acid solution, and then using perchloric acid. Acid acetic acid standard solution was used for potentiometric titration. Indicators can be used in this titration.

As the epoxy resin, commercially available products can be used. Specific examples of commercially available epoxy resins include amine-type epoxy resin (product name: jER630) manufactured by Mitsubishi Chemical Co., Ltd. and bisphenol F-type epoxy resin manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (product name: YDF-8170C), bisphenol A-type epoxy resin (product name: YD-128) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., naphthalene-type epoxy resin (product name) manufactured by DIC Co., Ltd. : HP-4032D) etc. The epoxy resin is not limited to these specific examples. The epoxy resin can be used alone, or two or more types can be used in combination. The content rate of the epoxy resin is not particularly limited. For example, the proportion in the solid content of the sealing resin composition is preferably 5% to 28% by mass, and more preferably 7% to 17% by mass. , and more preferably 10% by mass to 15% by mass.

- A hardening agent having at least one amine group in one molecule - (B) The hardening agent having at least one amine group in one molecule (hereinafter, sometimes referred to as a specific hardening agent) as the component (B) can be bonded to a ring through polymerization. It suffices to harden the oxy resin together. When forming the sealing resin composition, if the sealing resin composition has fluidity at room temperature (25°C), either a liquid or a solid may be used. Examples of specific curing agents include amine curing agents, carboxylic acid dihydrazide curing agents, and the like. From the viewpoint of fluidity, pot life, etc., the specific hardener is preferably an amine-based hardener.

Examples of amine-based hardeners include chain aliphatic amines, cyclic aliphatic amines, aliphatic aromatic amines, aromatic amines, and the like. In terms of heat resistance and electrical characteristics, aromatic amines are preferred, and more preferably It is an aromatic amine whose amine group is directly bonded to an aromatic ring and contains one or two aromatic rings in one molecule. The proportion of aromatic amines in the specific hardener is preferably 50 mass% to 100 mass%, more preferably 70 mass% to 100 mass%, and still more preferably 90 mass% to 100 mass%. Specific examples of the amine-based hardener include m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, and 3,5-diaminotoluene. Aromatic amine hardeners with an aromatic ring such as ethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, and 2,4-diaminoanisole; 4,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl Methyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5 Aromatic amine hardeners with two aromatic rings such as '-tetraethyl-4,4'-diaminodiphenylmethane; hydrolysis condensates of aromatic amine hardeners; polyoxytetramethylene di-amino groups Aromatic amine hardeners with polyether structures such as benzoate and polyoxytetramethylene di-p-aminobenzoate; condensates of aromatic diamines and epichlorohydrin; aromatic diamines and styrene reaction products, etc.

As the specific hardener, a commercially available product can be used. Specific examples of commercially available specific hardeners include amine hardeners manufactured by Nippon Kayaku Co., Ltd. (brand name: Kayahard-AA) and amine hardeners manufactured by Mitsubishi Chemical Co., Ltd. (Product name: jER Cure (registered trademark) 113, product name: jER Cure (registered trademark) W), etc., but the specific hardener is not limited to these specific examples. The specific hardener may be used alone, or two or more types may be used in combination.

The ratio of the equivalent number of the epoxy resin contained in the sealing resin composition to the equivalent number of the specific hardener is not particularly limited. In order to suppress each unreacted component to a small amount, it is preferable to set the ratio of the equivalent number of the epoxy resin to the equivalent number of the specific hardener (the equivalent number of the specific hardener/the equivalent number of the epoxy resin) to 0.6 to 1.4. The range is more preferably set to the range of 0.7 to 1.3, and still more preferably set to the range of 0.8 to 1.2.

The sealing resin composition may contain a hardener other than the specific hardener if necessary. Examples of other curing agents include phenol-based curing agents, acid anhydride-based curing agents, and imidazole-based curing agents.

-Inorganic filler- As the inorganic filler of component (C), (C1) a first inorganic filler with an average particle diameter of 0.1 μm to 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm to 80 nm may be used together. 2 Inorganic fillers. Examples of the inorganic filler include silica such as colloidal silica, hydrophobic silica, and spherical silica, inorganic particles such as talc, and organic particles. From the viewpoint of fluidity when applying the sealing resin composition and heat resistance of the cured product of the sealing resin composition, amorphous spherical silica is preferred. The content rate of the inorganic filler is not particularly limited. For example, the proportion in the solid content of the sealing resin composition is preferably 40% by mass to 85% by mass, and more preferably 46% by mass to 78% by mass. , and more preferably 50 mass% to 70 mass%.

The first inorganic filler of component (C1) imparts heat cycle resistance, moisture resistance, insulation, etc. to the cured product of the sealing resin composition, and reduces stress during curing of the sealing resin composition.

The average particle diameter of the first inorganic filler is 0.1 μm to 20 μm, preferably 0.2 μm to 10 μm, more preferably 0.2 μm to 8 μm, and still more preferably 0.3 μm to 5 μm. The specific surface area of the first inorganic filler is preferably 1 m ² /g to 30 m ² /g, and more preferably 2 m ² /g to 20 m ² /g from the viewpoint of fluidity.

The proportion of the first inorganic filler in the inorganic filler is preferably 70% by mass or more. In addition, the proportion of the first inorganic filler in the inorganic filler is preferably 99.7% by mass or less. The proportion of the first inorganic filler in the inorganic filler is more preferably 70 mass% to 99.7 mass%, and further preferably 75 mass% to 99.5 mass%.

As a method for measuring the specific surface area of the inorganic filler, the Brunauer-Emmett-Teller (BET) method is mainly used. The so-called BET method refers to the following gas adsorption method: inert gas molecules such as nitrogen (N ₂ ), argon (Ar), and krypton (Kr) are adsorbed on solid particles, and the solid particles are measured based on the amount of adsorbed gas molecules. Specific surface area. The specific surface area can be measured using a specific surface area pore distribution measuring device (for example, SA3100 manufactured by Beckman-Coulter).

As the first inorganic filler, a commercial product can be used. Specific examples of commercially available products of the first inorganic filler include spherical silica (product name: SO-E2) manufactured by Admatechs Co., Ltd., Admatechs Co., Ltd. The company's spherical silica (product name: SE2200), etc., but the first inorganic filler is not limited to these specific examples. Here, the average particle diameter of the first inorganic filler is measured with a dynamic light scattering Nanotrac particle size analyzer. In addition, the average particle diameter in this disclosure is a particle diameter corresponding to 50% of the volume accumulation from the small diameter side. The first inorganic filler may be used alone, or two or more types may be used in combination.

The first inorganic filler may have an organic group derived from manufacturing raw materials. Examples of organic groups that the first inorganic filler may have include alkyl groups such as methyl and ethyl. In addition, as the amorphous spherical silica, in terms of particle size controllability and purity, amorphous spherical silica produced by a sol-gel method is also preferred. Furthermore, as the silica, a silica-containing composition obtained by the manufacturing method described in Japanese Patent Application Laid-Open No. 2007-197655 can also be used.

By using the second inorganic filler of the (C2) component, the bleeding inhibitory effect is improved. The average particle diameter of the second inorganic filler is 10 nm to 80 nm, preferably 10 nm to 70 nm, more preferably 10 nm to 60 nm. When the average particle diameter of the second inorganic filler is 10 nm or more, the viscosity of the sealing resin composition tends to be less likely to increase and the fluidity is less likely to deteriorate.

The specific surface area of the second inorganic filler is preferably 20 m ² /g to 500 m 2 /g, and more preferably 50 ^{m 2 /} g to 300 m ² /g from the viewpoint of fluidity. As the second inorganic filler, a commercial product can be used. Specific examples of commercially available second inorganic fillers include inorganic fillers manufactured by Admatechs Co., Ltd. (product names: YA010C, YA050C, etc.) and inorganic fillers manufactured by Sakai Chemical Industry Co., Ltd. material (product name: Sciqas 0.05 μm), etc., but the second inorganic filler material is not limited to these specific examples. The second inorganic filler may be used alone, or two or more types may be used in combination.

The proportion of the second inorganic filler in the inorganic filler is preferably 0.3% by mass or more. In addition, the proportion of the second inorganic filler in the inorganic filler is preferably 30% by mass or less. The proportion of the second inorganic filler in the inorganic filler is more preferably 0.3% by mass to 30% by mass, and more preferably 0.5% by mass to 25% by mass. If the proportion of the second inorganic filler in the inorganic filler is within the above range, a sealing resin composition that exhibits a bleeding reducing effect and has excellent fluidity can be obtained. In one aspect, the proportion of the second inorganic filler in the inorganic filler is preferably 10 mass% to 30 mass%, more preferably 12 mass% to 27 mass%, and further preferably 15 mass% to 25 mass%. Mass %.

As the second inorganic filler, one whose surface of the particles has been treated with an organic group in advance may be used. By treating the surface of the particles in advance with an organic group, it is preferable in terms of improving the adhesion to semiconductor wafers, organic substrates, etc. and improving the toughness of the cured product of the sealing resin composition.

The ratio of the average particle diameter of the first inorganic filler to the average particle diameter of the second inorganic filler (average particle diameter of the first inorganic filler/average particle diameter of the second inorganic filler) is preferably 5 to 100, more preferably Preferably, it is 7-75, and more preferably, it is 10-50.

Whether the inorganic filler includes both the first inorganic filler and the second inorganic filler can be confirmed, for example, by determining the volume-based particle size distribution (frequency distribution) of the inorganic filler. Specifically, when there are peaks in the volume-based frequency distribution of the inorganic filler in the range of 0.1 μm to 20 μm and in the range of 10 nm to 80 nm, it can be said that the inorganic filler includes the first inorganic Both the filler and the second inorganic filler. In addition, the confirmation method is not limited to the above-mentioned method. In addition, the method for determining the proportion of the first inorganic filler or the second inorganic filler in the inorganic filler is not particularly limited. For example, the ratio of the first inorganic filler or the second inorganic filler can be determined as follows: the volume-based particle size distribution (frequency distribution) of the inorganic filler is determined, and the ratio between the peak corresponding to the first inorganic filler and The valleys corresponding to the peaks of the second inorganic filler are divided into two parts, and the volume of the particles contained in each of the divided ranges is divided by the total volume of the inorganic filler. When the composition of the sealing resin composition is clear, the proportion of the first inorganic filler or the second inorganic filler in the inorganic filler can be determined based on the composition of the sealing resin composition. In addition, the calculation method is not limited to the above-mentioned method.

The ratio of the mass of the inorganic filler to the mass of the solid component multiplied by the specific surface area of the inorganic filler is 4 m ² /g or more, preferably 4 m ² /g to 30 m ² /g, more preferably The range is 5 m ² /g to 26 m ² /g, and more preferably, the range is 6 m ² /g to 24 m ² /g. If the ratio of the mass of the inorganic filler to the mass of the solid content multiplied by the specific surface area of the inorganic filler is within the above range, a resin composition that exhibits a bleeding reduction effect and has excellent fluidity can be obtained. Here, the "specific surface area of the inorganic filler" refers to the weighted average of the first inorganic filler and the second inorganic filler. When an inorganic filler other than the first inorganic filler and the second inorganic filler is used together as the inorganic filler, the specific surface area of the inorganic filler refers to the first inorganic filler, the second inorganic filler and others. Weighted average of inorganic fillers. In addition, the "solid content mass" refers to the mass of the solid content contained in the sealing resin composition, and refers to the remaining components after removing volatile components such as organic solvents from the sealing resin composition.

-Rubber additive- From the viewpoint of relaxing the stress of the cured product of the sealing resin composition, the sealing resin composition is preferably a rubber additive containing the component (D). Examples of rubber additives include acrylic rubber, urethane rubber, silicone rubber, butadiene rubber, and the like. Rubber additives can be used if they are solid at room temperature (25°C). The form is not particularly limited, and those in granular or granular form can be used. When the rubber additive is in the form of particles, for example, the average particle diameter is preferably 0.01 μm to 20 μm, more preferably 0.02 μm to 10 μm, and still more preferably 0.03 μm to 5 μm. Rubber additives can also be used in liquid form at normal temperature (25°C). Examples of liquid rubber additives include polybutadiene, butadiene×acrylonitrile copolymer, polyisoprene, polypropylene oxide, polydiorganosiloxane, and the like. When the rubber additive is solid at normal temperature (25°C), it is preferably heated and dissolved in an epoxy resin or a specific hardener before use. In addition, rubber additives can be used for those having a terminal group that reacts with an epoxy group. The rubber additive having a group that reacts with the epoxy group at the end may be solid or liquid at normal temperature (25°C), or may be in any form. As the rubber additive, commercially available products can be used. Specific examples of commercially available rubber additives include CTBN1300, ATBN1300-16, CTBN1008-SP, etc. manufactured by Ube Kosan Co., Ltd., and silicone rubber powder manufactured by Toray Dow Corning Co., Ltd. (product name: AY42-119, etc.), rubber powder (product name: XER81, etc.) manufactured by JSR Co., Ltd., but the rubber additive is not limited to these specific examples. In addition, the rubber additive may be used alone, or two or more types may be used in combination.

-Coupling agent- The sealing resin composition may contain the coupling agent of component (E). It is preferable from the viewpoint of the adhesiveness of the sealing resin composition if the sealing resin composition contains a coupling agent. The coupling agent is not particularly limited and can be appropriately selected and used from those known in the past. For example, aminosilane, epoxysilane, mercaptosilane, alkylsilane, and ureidosilane having at least one selected from the group consisting of a primary amine group, a secondary amine group, and a tertiary amine group, Silane compounds such as vinylsilane; titanate compounds, etc. Among these, from the viewpoint of the adhesiveness of the sealing resin composition, an epoxy silane compound is preferred. As the coupling agent, commercially available products can be used. Specific examples of commercially available coupling agents include KBM-403, KBE-903, and KBE-9103 manufactured by Shin-Etsu Chemical Industry Co., Ltd., but the coupling agent is not limited to these specific examples. The coupling agent may be used alone, or two or more types may be used in combination.

-Other components- The sealing resin composition may optionally contain pigments such as thixotropic agents and carbon black to improve workability, dyes, ion scavengers, and defoaming agents within the scope that does not impair the purpose of this disclosure. , leveling agents, antioxidants, reactive diluents, organic solvents and other ingredients.

The sealing resin composition can be obtained, for example, by stirring an epoxy resin, a specific hardener, an inorganic filler, and optionally other components in batches or separately, while heating them as needed. , melting, mixing, dispersing, etc. In particular, when the specific hardening agent is solid, if the specific hardening agent is prepared in a solid state, the viscosity may increase and the workability may decrease. Therefore, it is preferable to liquefy the specific hardening agent by heating in advance. use. The device for mixing, stirring, dispersing, etc. of these components is not particularly limited, and examples thereof include: a sand mixer equipped with a stirring device, a heating device, etc., a three-roller mill, a ball mill, a planetary mixer, a bead mixer, etc. Mill etc. The components are mixed and kneaded using these devices and degassed if necessary, thereby obtaining a sealing resin composition.

The viscosity of the sealing resin composition is not particularly limited. Among them, from the viewpoint of high fluidity, at 25°C, it is preferably 0.1 Pa·s to 50.0 Pa·s, more preferably 0.1 Pa·s to 20.0 Pa·s, and still more preferably 0.1 Pa·s. ~10.0 Pa·s. In addition, the viscosity of the sealing resin composition was measured at 25°C using an E-type viscometer (cone angle 3°, rotation speed 10 rpm).

In addition, when the sealing resin composition is used for applications such as underfill materials, the sealing resin composition is filled into a narrow space of several tens to several hundred microns at a temperature near 100°C to 120°C. As an index of ease of filling, the viscosity at 110°C is preferably 0.20 Pa·s or less, more preferably 0.15 Pa·s or less. In addition, the viscosity of the sealing resin composition at 110°C was measured with a rheometer AR2000 (manufactured by TA Instruments, aluminum cone 40 mm, cutting speed 32.5/sec).

In addition, in the sealing resin composition, the thixotropic index is the ratio of the viscosity at 1.5 rpm and the viscosity at 10 rpm measured using an E-type viscometer at 25°C [(1.5 viscosity at 10 rpm)/(viscosity at 10 rpm)] is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. If the thixotropic index is within the above range, the fillet formability in the use of underfill materials will be further improved. Furthermore, the viscosity and thixotropic index of the sealing resin composition can be set to a desired range by appropriately selecting the composition of the epoxy resin, the content rate of the inorganic filler, and the like.

The curing conditions of the sealing resin composition are not particularly limited, but are preferably heated at 80°C to 165°C for 1 minute to 150 minutes.

<Electronic component device> 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 cured product of the sealing resin composition of the present disclosure. , arranged in the gap between the substrate and the electronic component. The electronic component device of the present disclosure can be obtained by sealing the electronic component using the sealing resin composition of the present disclosure. The electronic component device disclosed in the present disclosure has excellent temperature cycle resistance by sealing the electronic component with the sealing resin composition.

Examples of electronic component devices include semiconductor wafers, transistors, diodes, and thyristors mounted on substrates with circuit layers such as lead frames, wired conveyor tapes, rigid wiring boards, flexible wiring boards, glass, and silicon wafers. and other active components; electronic components such as capacitors, resistors, resistor arrays, coils, switches and other passive components, and an electronic component device obtained by sealing the required parts with the sealing resin composition of the present disclosure. In particular, one of the objects to which the present disclosure is applicable includes a semiconductor device in which a semiconductor element is flip-chip bonded to wiring formed on a rigid wiring board, a flexible wiring board, or glass through bump connection. Specific examples include flip chip ball grid array (BGA), land grid array (LGA), chip on film (Chip On Film, COF) and other electronic component devices.

The sealing resin composition of the present disclosure is suitable for use as an underfill material for flip-chips with excellent reliability. A particularly suitable field for flip-chips to which the sealing resin composition of the present disclosure can be applied is that the bump material connecting the wiring board and the semiconductor element uses lead-free solder such as Sn-Ag-Cu system instead of the conventional lead-containing solder. Flip chip semiconductor components. The sealing resin composition of the present disclosure can also maintain good reliability with respect to flip-chips that are bump-connected using lead-free solder that has brittle physical properties compared to conventional lead solder. In addition, when a chip-size package such as a wafer-level CSP is mounted on a substrate, reliability can also be improved by applying the sealing resin composition of the present disclosure.

<Manufacturing method of an electronic component device> The method of manufacturing an electronic component device of the present disclosure includes using the sealing resin composition of the present disclosure to connect a substrate having a circuit layer and a substrate disposed on the substrate and electrically connected to the circuit layer. Steps for sealing electronic parts. The step of sealing a substrate with a circuit layer and an electronic component using the sealing resin composition of the present disclosure is not particularly limited. For example, the post-injection method can be used to connect the electronic component to a substrate with a circuit layer, and then use the capillary phenomenon to apply the sealing resin composition to the gap between the electronic component and the substrate, and then perform a curing reaction of the sealing resin composition; As well as the pre-coating method, the sealing resin composition of the present disclosure is previously applied to the surface of at least one of the substrate and the electronic component having the circuit layer, and the electronic components are connected to the substrate by thermocompression bonding. The electronic components are processed in batches. The curing reaction of the resin composition for connecting and sealing parts and substrates. Examples of methods for applying the sealing resin composition include casting, dispensing, and printing.

By using the sealing resin composition of the present disclosure, electronic component devices such as flip-chip mounting bodies in which leakage is suppressed can be easily manufactured. [Example]

Hereinafter, the present invention will be described based on Examples, but the present invention is not limited to the following Examples. In addition, in the following examples, unless otherwise specified, parts and % represent parts by mass and % by mass.

Seals of Examples 1 to 9 and Comparative Examples 1 to 7 were prepared by mixing each component so as to have the composition shown in Table 1 and Table 2, kneading and dispersing it using a three-roller and vacuum sand mixer. Use resin composition. In addition, the blending unit in the table is parts by mass, and "-" means "not blended". Furthermore, the content rate (mass %) of the inorganic filler in the sealing resin composition is calculated based on the blending amount of each component.

(Examples 1 to 9, Comparative Examples 1 to 7) As the epoxy resin, a bisphenol F-type epoxy resin (Epoxy Resin 1; manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name "YDF") was prepared. -8170C", epoxy equivalent: 160 g/eq) and trifunctional amine-type epoxy resin with epoxy group (Epoxy Resin 2; manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER630", epoxy equivalent: 95 g/eq).

As a specific hardener, a diaminotoluene-type amine hardener (Amine Hardener 1; manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER Cure W") and a diaminodiphenylmethane-type amine hardener are prepared. Agent (amine hardener 2; manufactured by Nippon Kayaku Co., Ltd., trade name "Kayahard-AA").

As an inorganic filler, an inorganic filler having an average particle diameter of silica particles of 0.5 μm and a specific surface area of 4.5 m ² /g was prepared (Inorganic filler 1: manufactured by Admatechs Co., Ltd., trade name "SE2200-SEJ"), an inorganic filler with an average particle diameter of 50 nm and a specific surface area of 66 ^m2 /g (Inorganic filler 2: manufactured by Admatechs Co., Ltd., trade name "YA050C-SZ2"), Inorganic filler with an average particle diameter of 10 nm and a specific surface area of 280 m ² /g (Inorganic filler 3: manufactured by Admatechs Co., Ltd., trade name "YA010C-SZ2"), with an average particle diameter of 0.3 μm and Inorganic filler with a specific surface area of 14 m ² /g (Inorganic filler 4: manufactured by Admatechs Co., Ltd., trade name "SE1050"), an average particle diameter of 0.3 μm, and a specific surface area of 15 m ² /g Inorganic filler (Inorganic filler 5: manufactured by Admatechs Co., Ltd., trade name "SE1050-SET"), an inorganic filler with an average particle diameter of 0.3 μm and a specific surface area of 16 m ² /g (Inorganic filler Material 6: Inorganic filler manufactured by Admatechs Co., Ltd., trade name "SE1030-SET"), with an average particle diameter of 0.15 μm and a specific surface area of 30 m ² /g (Inorganic filler 7: Nippon Shokubai Co., Ltd., trade name "KE-S10") and an inorganic filler with an average particle diameter of 0.15 μm and a specific surface area of 30 m ² /g (Inorganic filler 8: manufactured by Nippon Shokubai Co., Ltd., trade name "KE- S10-HG").

Regarding the sealing resin composition thus obtained, each characteristic was evaluated as follows. In addition, each numerical value is shown in Table 1 and Table 2 below.

(1) Fluidity: Viscosity and thixotropic index Use an E-type viscometer (cone angle 3°, rotation speed 10 rpm) to measure the viscosity of the sealing resin composition at 25°C (normal temperature viscosity, Pa·s) . In addition, the thixotropic index at 25°C is set as the ratio of the viscosity at 1.5 rpm to the viscosity at 10 rpm [(viscosity at 1.5 rpm)/(viscosity at 10 rpm) viscosity)]. The viscosity (Pa·s) at 110°C was measured using a rheometer AR2000 (aluminum cone 40 mm, cutting speed 32.5/sec).

(2) Heat resistance: glass transition temperature (Tg), coefficient of thermal expansion (CTE) using a thermomechanical analysis device (manufactured by TA Instrument Japan Co., Ltd., trade name TMAQ400), under a load of 15 g. The test piece (f4 mm × 20 mm) prepared by hardening the sealing resin composition at 165°C for 2 hours was measured at a temperature of -50°C to 220°C and a temperature rise rate of 5°C/min. Determination. In addition, let the thermal expansion coefficient in the temperature range below Tg be CTE1, and let the thermal expansion coefficient in the temperature range above Tg be CTE2. Tg and CTE represent thermal stability, and Tg is preferably about 100°C to 130°C. The lower CTE1 and CTE2, the better.

(3) Bleeding: To measure the bleeding length, subject the solder resist substrate to Ar ₂ plasma treatment (400 W, 2 minutes), and use a 20 G probe to eject 30 mg of the sealing resin composition filled in the syringe until the The Ar ₂ plasma treated solder resist substrate was bonded and hardened at 150°C for 120 minutes. After hardening, optical microscopy was used to determine the length of the exudate. As a substrate, a solder resist (PSR-4000-AUS703, manufactured by Taiyo Ink Manufacturing Co., Ltd.) formed on FR-4 (MRC-E-679, manufactured by Hitachi Chemical Co., Ltd.) was used. The bleeding length is preferably 500 μm or less, more preferably 400 μm or less, and still more preferably 350 μm or less.

[Table 1]

[Table 2]

In Table 1 and Table 2, "the content rate of the second inorganic filler" refers to the proportion of the second inorganic filler in the inorganic filler. In Tables 1 and 2, "specific surface area × ratio of inorganic filler" means "the ratio of the mass of the inorganic filler to the mass of the solid content multiplied by the specific surface area of the inorganic filler."

From the results in Table 1 and Table 2, it is clear that the sealing resin compositions of Examples 1 to 9 are superior in bleeding out compared with the sealing resin compositions of Comparative Examples 1 to 7.

All documents, patent applications, and technical specifications described in this specification are incorporated by reference into this specification to the same extent as if each individual document, patent application, or technical specification was specifically and individually stated to be incorporated by reference. middle.

without

without

Claims (23)

A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the (C1) average The proportion of the first inorganic filler with a particle size of 0.1 μm to 20 μm in the (C) inorganic filler is 70% by mass or more. The sealing resin composition described in item 1 of the patent application, wherein the viscosity at 25°C is 0.1 Pa. s~50.0Pa． s. The sealing resin composition according to claim 1, wherein the first inorganic filler (C1) with an average particle diameter of 0.1 μm to 20 μm contains silica. The sealing resin composition according to claim 1, wherein the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm contains silica. The sealing resin composition described in item 1 of the patent application, which , the content rate of the (C) inorganic filler is 40% by mass to 85% by mass. The sealing resin composition described in item 1 of the patent application, wherein the first inorganic filler (C1) with an average particle diameter of 0.1 μm ~ 20 μm has a specific surface area of 1 m ² /g ~ 30 m ² /g . As for the sealing resin composition described in claim 1, the specific surface area of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm is 20 m ² /g to 500 m ² /g. The sealing resin composition described in item 1 of the patent application, wherein the thixotropic index at 25°C is 0.5~1.5. The sealing resin composition according to claim 1, wherein the hardener (B) having at least one amine group in one molecule contains an aromatic amine. The sealing resin composition according to claim 9, wherein the aromatic amine has an amine group directly bonded to an aromatic ring and contains one or two of the aromatic rings in one molecule. The resin composition for sealing as described in item 1 of the patent application, wherein the average particle diameter (C1) of the first inorganic filler is 0.1 μm to 20 μm and the average particle diameter of the (C2) The ratio of the average particle diameter of the second inorganic filler, which is C1/C2, is 10 nm to 80 nm, and is 10 to 50. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) The first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) the second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler accounts for the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the sealing resin composition The viscosity of the substance at 25℃ is 0.1Pa. s~50.0Pa． s. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the (C1) average The first inorganic filler with a particle diameter of 0.1 μm to 20 μm contains silica. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10nm~80nm in the (C) inorganic filler is 10%~30% by mass, and the average particle size of (C2) The second inorganic filler having a particle diameter of 10 nm to 80 nm contains silica. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the (C) inorganic filler The filler content is 40% by mass to 85% by mass. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the (C1) average The first inorganic filler with a particle diameter of 0.1 μm to 20 μm has a specific surface area of 1 m ² /g to 30 m ² /g. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the (C2) average particle size The specific surface area of the second inorganic filler having a particle diameter of 10 nm to 80 nm is 20 m ² /g to 500 m ² /g. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the sealing resin composition The thixotropic index of the substance at 25℃ is 0.5~1.5. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the (B) Hardeners having at least one amine group in a molecule include aromatic amines. The sealing resin composition according to claim 19, wherein the aromatic amine has an amine group directly bonded to an aromatic ring and contains one or two of the aromatic rings in one molecule. A sealing resin composition comprising (A) epoxy resin, (B) a hardener having at least one amine group in one molecule, and (C) an inorganic filler, the (C) inorganic filler comprising (C1 ) a first inorganic filler with an average particle diameter of 0.1 μm ~ 20 μm and (C2) a second inorganic filler with an average particle diameter of 10 nm ~ 80 nm, the mass of the (C) inorganic filler in the mass of the solid component The value obtained by multiplying the ratio by the specific surface area of the (C) inorganic filler is 4.0 m ² /g or more, and the viscosity of the sealing resin composition at 110°C is 0.20 Pa. s or less, the proportion of the second inorganic filler (C2) with an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 10 mass% to 30 mass%, and the (C1) average The ratio of the average particle diameter of the first inorganic filler with a particle diameter of 0.1 μm to 20 μm and the average particle diameter of the second inorganic filler with an average particle diameter of (C2) of 10 nm to 80 nm, that is, C1/C2, is 10 to 50 . An electronic component device, which includes: a substrate having a circuit layer; electronic components arranged on the substrate and electrically connected to the circuit layer; and The cured product of the sealing resin composition according to any one of claims 1 to 21 is disposed in a gap between the substrate and the electronic component. A method of manufacturing an electronic component device, which includes using a sealing resin composition as described in any one of items 1 to 21 of the patent application to dispose a substrate having a circuit layer on the substrate and connect it with the Describes the steps for sealing electronic components that are electrically connected to the circuit layer.