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

Abstract

The present invention relates to a resin composition for sealing, an electronic component device, and a method for manufacturing the electronic component device, the resin composition for sealing comprising (A) an epoxy resin, (B) a curing agent having at least one amino group in one molecule, and (C) an inorganic filler, the inorganic filler (C) contains (C1) a first inorganic filler having an average particle diameter of 0.3-5 [mu] m and (C2) a second inorganic filler having an average particle diameter of 10-80 nm, and the value obtained by multiplying the specific surface area of the inorganic filler (C) by the proportion of the mass of the inorganic filler (C) in the mass of the solid content is 4.0 m2 / g or more. The resin composition for sealing according to the present invention can suppress leakage.

Description

[0001] This application is a divisional application of a patent application for an invention titled "Resin Composition for Sealing, Electronic Component Device, and Method for Manufacturing Electronic Component Device", with an international filing date of September 26, 2017, an international application number of PCT / JP2017 / 034810, and a Chinese application number of 201780063091.5. Technical Field

[0002] The present invention relates to a resin composition for sealing, an electronic component device, and a method for manufacturing an electronic component device. Background Art

[0003] In recent years, in order to cope with further high density of wirings and the like in electronic devices, flip chip bonding is used as a mounting method for semiconductor chips adopting system-in-package. A package obtained by flip chip bonding is called a flip chip package (FC-PKG). Generally, in an FC-PKG, a liquid resin composition called an underfill material is used to seal a gap between a semiconductor chip and a substrate.

[0004] In recent years, the demand for FC-PKGs for mobile device applications has been increasing, and in particular, semiconductor modules adopting small flip chip-chip scale packages (FC-CSPs) have been increasing. Currently, the PKG size of FC-CSPs has reached about 20 mm or less × 20 mm or less × 2 mm, and further miniaturization is required.

[0005] Here, as one of the related problems of a semiconductor underfill material for sealing a gap between a semiconductor chip and a substrate, bleed can be cited. Bleed in an FC-PKG refers to a phenomenon in which a liquid component in a semiconductor sealing material as a liquid resin composition spreads and oozes out on the surface of a solder resist applied on a substrate under a semiconductor chip. If bleed occurs, it may sometimes contaminate a connection circuit near the position where the FC-PKG is disposed.

[0006] Therefore, in recent years, various studies have been conducted to avoid bleed on the surface of the solder resist. To solve bleed, a liquid sealing resin composition containing an acrylic-siloxane copolymer (for example, refer to Patent Document 1), a liquid sealing resin composition containing a silicone oil containing an amino group (for example, refer to Patent Document 2), and a liquid sealing resin composition containing a liquid organosilicon compound having a polyether group and a liquid organosilicon compound having an amino group (for example, refer to Patent Document 3) have been reported.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2011-6618

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 2010-192525

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 2012-107149 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] However, there is a concern that the addition of a silicone copolymer or a silicone compound may cause a decrease in the surface tension of the liquid resin composition. When the liquid resin composition is used as an underfill material, a decrease in the surface tension of the liquid resin composition may cause deterioration of the encapsulation injectability. Therefore, a material that can suppress leakage without relying on a silicone copolymer or a silicone compound is required.

[0014] The present invention has been made in view of the above circumstances, and an object thereof is to provide a sealing resin composition that can suppress leakage, an electronic component device using the sealing resin composition, and a method for manufacturing the same.

[0015] Means for Solving the Problems

[0016] Specific means for solving the above problems are as follows.

[0017] <1> A sealing resin composition comprising (A) an epoxy resin, (B) a curing agent having at least 1 amino group in 1 molecule, and (C) an inorganic filler, wherein the (C) inorganic filler comprises (C1) a first inorganic filler having an average particle diameter of 0.1 μm to 20 μm and (C2) a second inorganic filler having an average particle diameter of 10 nm to 80 nm, and the value obtained by multiplying the specific surface area of the (C) inorganic filler by the proportion of the mass of the (C) inorganic filler in the solid component mass is 4.0 m 2 / g or more.

[0018] <2> The sealing resin composition according to <1>, wherein the viscosity at 110 °C is 0.20 Pa·s or less.

[0019] <3> The sealing resin composition according to <1> or <2>, wherein the proportion of the (C2) second inorganic filler having an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 0.3 mass% or more.

[0020] <4> The sealing resin composition according to any one of <1> to <3>, wherein the proportion of the (C2) second inorganic filler having an average particle diameter of 10 nm to 80 nm in the (C) inorganic filler is 30 mass% or less.

[0021] <5> The resin composition for sealing according to any one of <1> to <4>, wherein the proportion of the above-mentioned (C1) first inorganic filler having an average particle size of 0.1 μm to 20 μm in the above-mentioned (C) inorganic filler is 70% by mass or more.

[0022] <6> The resin composition for sealing according to any one of <1> to <5>, wherein the viscosity at 25 °C is 0.1 Pa·s to 50.0 Pa·s.

[0023] <7> The resin composition for sealing according to any one of <1> to <6>, wherein the above-mentioned (C1) first inorganic filler having an average particle size of 0.1 μm to 20 μm contains silica.

[0024] <8> The resin composition for sealing according to any one of <1> to <7>, wherein the above-mentioned (C2) second inorganic filler having an average particle size of 10 nm to 80 nm contains silica.

[0025] <9> The resin composition for sealing according to any one of <1> to <8>, wherein the content rate of the above-mentioned (C) inorganic filler is 40% by mass to 85% by mass.

[0026] <10> The resin composition for sealing according to any one of <1> to <9>, wherein the specific surface area of the above-mentioned (C1) first inorganic filler having an average particle size of 0.1 μm to 20 μm is 1 m 2 / g to 30 m 2 / g.

[0027] <11> The resin composition for sealing according to any one of <1> to <10>, wherein the specific surface area of the above-mentioned (C2) second inorganic filler having an average particle size of 10 nm to 80 nm is 20 m 2 / g to 500 m 2 / g.

[0028] <12> The resin composition for sealing according to any one of <1> to <11>, wherein the thixotropic index at 25 °C is 0.5 to 1.5.

[0029] <13> An electronic component device, comprising: a substrate having a circuit layer; an electronic component disposed on the above-mentioned substrate and electrically connected to the above-mentioned circuit layer; and a cured product of the resin composition for sealing according to any one of <1> to <12> disposed in the gap between the above-mentioned substrate and the above-mentioned electronic component.

[0030] <14>A method for manufacturing an electronic component device, comprising: a step of sealing a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer with the sealing resin composition according to any one of <1> to <12>.

[0032] Advantages of the Invention

[0033] According to the present invention, there are provided a sealing resin composition capable of suppressing leakage, an electronic component device using the sealing resin composition, and a method for manufacturing the same. Detailed Description of the Invention

[0034] Hereinafter, modes 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 specified. The same applies to numerical values and their ranges, which are not intended to limit the present invention.

[0035] In this specification, the term "step" includes not only steps independent of other steps but also steps that, even if not clearly distinguishable from other steps, are included as long as the purpose of the step is achieved.

[0036] In this specification, a numerical range indicated by "~" includes the numerical values before and after "~" and regards them as the minimum value and the maximum value, respectively.

[0037] In the numerical ranges described in stages in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerically described range. In addition, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

[0038] In this specification, when there are two or more substances corresponding to each component in the composition, unless otherwise specified, the content rate of each component in the composition refers to the total content rate of the two or more substances present in the composition.

[0039] In this specification, when there are two or more kinds of particles corresponding to each component in the composition, unless otherwise specified, the particle size of each component in the composition refers to a value related to the mixture of the two or more kinds of particles present in the composition.

[0040] In this specification, with respect to the term "layer", in addition to including the case where it is formed over the entire area when observing the area where the layer is present, it also includes the case where it is formed only in a part of the area.

[0041] <Sealing Resin Composition>

[0042] The resin composition for sealing of the present disclosure contains (A) an epoxy resin, (B) a curing agent having at least 1 amino group in 1 molecule, and (C) an inorganic filler. The (C) inorganic filler contains (C1) a first inorganic filler having an average particle diameter of 0.1 μm to 20 μm and (C2) a second inorganic filler having an average particle diameter of 10 nm to 80 nm. The value obtained by multiplying the specific surface area of the (C) inorganic filler by the proportion of the mass of the (C) inorganic filler in the solid component mass is 4.0 m 2 / g or more.

[0043] Details of each component constituting the resin composition for sealing will be described below.

[0044] - Epoxy resin -

[0045] The epoxy resin of the component (A) imparts curability and adhesiveness to the resin composition for sealing, and imparts heat resistance and durability to the cured product of the resin composition for sealing. The epoxy resin is preferably a liquid epoxy resin. In the present disclosure, as long as it is within the range where leakage can be suppressed, a solid epoxy resin may also be used in combination with the liquid epoxy resin.

[0046] It should be noted that the 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 above viscosity, specifically, using an EHD-type (cone angle 3°, cone diameter 28 mm) E-type viscometer, at a measurement temperature of 25°C, a sample volume of 0.7 ml, and based on setting the rotation speed in combination with the predicted viscosity of the sample under the following conditions, the value after 1 minute from the start of measurement is used as the measurement value.

[0047] (1) When the predicted viscosity is 100 Pa·s to 1000 Pa·s: rotation speed 0.5 revolutions per minute

[0048] (2) When the predicted viscosity is less than 100 Pa·s: rotation speed 5 revolutions per minute

[0049] In addition, the solid epoxy resin refers to an epoxy resin that is solid at normal temperature (25°C).

[0050] The type of the epoxy resin is not particularly limited. Examples of the epoxy resin include: naphthalene-type epoxy resins; diglycidyl ether-type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; epoxy resins obtained by epoxidizing phenolic resins of phenols and aldehydes, typified by o-cresol novolac-type epoxy resins; glycidyl ester-type epoxy resins obtained by the reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; glycidyl amine-type epoxy resins obtained by the reaction of amine compounds such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin, and the like.

[0051] Regarding the epoxy equivalent of the epoxy resin, from the viewpoint of viscosity adjustment, it 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.

[0052] The epoxy equivalent of the epoxy resin can be measured as follows: The weighed epoxy resin is dissolved in a solvent such as methyl ethyl ketone, acetic acid and a tetraethylammonium bromide acetic acid solution are added, and then potentiometric titration is carried out using a perchloric acid acetic acid standard solution, whereby the measurement is performed. An indicator can also be used in this titration.

[0053] As the epoxy resin, commercially available products can be used. Specific examples of commercially available products of epoxy resins include: amine-type epoxy resin (product name: jER630) manufactured by Mitsubishi Chemical Corporation, bisphenol F-type epoxy resin (product name: YDF-8170C) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A-type epoxy resin (product name: YD-128) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthalene-type epoxy resin (product name: HP-4032D) manufactured by DIC Corporation, and the like. The epoxy resin is not limited to these specific examples. The epoxy resin can be used alone or in combination of two or more.

[0054] The content rate of the epoxy resin is not particularly limited. For example, as the proportion in the solid content of the sealing resin composition, it is preferably 5% by mass to 28% by mass, more preferably 7% by mass to 17% by mass, and still more preferably 10% by mass to 15% by mass.

[0055] - Curing agent having at least 1 amino group in 1 molecule -

[0056] The curing agent having at least 1 amino group in 1 molecule of the component (B) (hereinafter sometimes referred to as a specific curing agent) is only required to be a curing agent that cures by polymerization together with the epoxy resin, and as long as the sealing resin composition has fluidity at room temperature (25°C) when the sealing resin composition is prepared, liquid or solid curing agents can be used.

[0057] As the specific curing agent, amine curing agents, carboxylic dihydrazide curing agents, etc. may be mentioned. From the viewpoints of fluidity, pot life, etc., an amine curing agent is preferably used as the specific curing agent.

[0058] As the amine curing agent, linear aliphatic amines, cycloaliphatic amines, aliphatic aromatic amines, aromatic amines, etc. may be mentioned. From the viewpoints of heat resistance and electrical properties, aromatic amines are preferably used.

[0059] Specific examples of the amine curing agent include: aromatic amine curing agents having 1 aromatic ring such as m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole, etc.; aromatic amine curing agents having 2 aromatic rings such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-methylenebis(2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, etc.; hydrolysis condensates of aromatic amine curing agents; aromatic amine curing agents having a polyether structure such as polytetramethylene oxide di-p-aminobenzoate, polytetramethylene oxide diparaaminobenzoate, etc.; condensates of aromatic diamines and epichlorohydrin; reaction products of aromatic diamines and styrene, etc.

[0060] As the specific curing agent, commercially available products can be used. Specific examples of the commercially available products of the specific curing agent include: amine curing agent manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard-AA), amine curing agent manufactured by Mitsubishi Chemical Corporation (product name: jER cure (registered trademark) 113, product name: jER cure (registered trademark) W), etc. However, the specific curing agent is not limited to these specific examples. The specific curing agent can be used alone or in combination of two or more.

[0061] The ratio of the equivalent number of the epoxy resin contained in the resin composition for sealing to the equivalent number of the specific curing agent is not particularly limited. In order to suppress the unreacted components of each 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 curing agent (equivalent number of the specific curing agent / equivalent number of the epoxy resin) in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3, and further preferably in the range of 0.8 to 1.2.

[0062] The sealing resin composition may contain, as required, a curing agent other than the specific curing agent. Examples of the other curing agents include phenolic curing agents, acid anhydride curing agents, and imidazole curing agents.

[0063] - Inorganic filler -

[0064] As the inorganic filler of component (C), a first inorganic filler having an average particle size of 0.1 μm to 20 μm and a second inorganic filler having an average particle size of 10 nm to 80 nm are used in combination.

[0065] 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 viewpoints of the fluidity during coating of the sealing resin composition and the heat resistance of the cured product of the sealing resin composition, amorphous spherical silica is preferred.

[0066] The content rate of the inorganic filler is not particularly limited. For example, as the proportion in the solid content of the sealing resin composition, it is preferably 40% by mass to 85% by mass, more preferably 46% by mass to 78% by mass, and still more preferably 50% by mass to 70% by mass.

[0067] The first inorganic filler of component (C1) imparts heat cycle resistance, moisture resistance, insulation properties, etc. to the cured product of the sealing resin composition, and reduces the stress during curing of the sealing resin composition.

[0068] The average particle size 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.

[0069] Regarding the specific surface area of the first inorganic filler, from the viewpoint of fluidity, it is preferably 1 m 2 / g to 30 m 2 / g, more preferably 2 m 2 / g to 20 m 2 / g.

[0070] 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% by mass to 99.7% by mass, and still more preferably 75% by mass to 99.5% by mass.

[0071] As a method for measuring the specific surface area of an inorganic filler, the BET method is mainly used. The BET method refers to a gas adsorption method in which solid particles adsorb inert gas molecules such as nitrogen (N2), argon (Ar), and krypton (Kr), and the specific surface area of the solid particles is measured from the amount of the adsorbed gas molecules. The measurement of the specific surface area can be carried out using a specific surface area and pore size distribution measuring device (for example, manufactured by Beckman Coulter, SA3100).

[0072] As the first inorganic filler, commercially available products can be used. Specific examples of commercially available products of the first inorganic filler include spherical silica manufactured by Admatechs Co., Ltd. (product name: SO-E2), spherical silica manufactured by Admatechs Co., Ltd. (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 using a dynamic light scattering type Nanotrac particle size analyzer. It should be noted that the average particle diameter in the present disclosure is set to the particle diameter corresponding to 50% of the volume accumulation from the small particle size side. The first inorganic filler can be used alone or in combination of two or more.

[0073] The first inorganic filler may have an organic group derived from a manufacturing raw material. Examples of the organic group that the first inorganic filler may have include alkyl groups such as methyl and ethyl.

[0074] In addition, as amorphous spherical silica, from the viewpoints of particle diameter controllability and purity, amorphous spherical silica manufactured by the sol-gel method is also preferred. It should be noted that as silica, a silica-containing composition obtained by the manufacturing method described in Japanese Patent Laid-Open No. 2007-197655 can also be used.

[0075] By using the second inorganic filler of the component (C2), the suppression effect of leakage is improved. The average particle diameter of the second inorganic filler is 10 nm to 8 nm, preferably 10 nm to 70 nm, more preferably 10 nm to 60 nm. If the average particle diameter of the second inorganic filler is 10 nm or more, the viscosity of the sealing resin composition is not likely to increase and the fluidity is not likely to deteriorate.

[0076] Regarding the specific surface area of the second inorganic filler, from the viewpoint of fluidity, it is preferably 20 m 2 / g to 500 m 2 / g, more preferably 50 m 2 / g to 300 m 2 / g.

[0077] As the second inorganic filler, commercially available products can be used. Specific examples of commercially available products of the second inorganic filler include inorganic fillers manufactured by Admatechs Co., Ltd. (product names: YA010C, YA050C, etc.), inorganic fillers manufactured by Sakai Chemical Industry Co., Ltd. (product name: Sciqas0.05μm), etc. The second inorganic filler is not limited to these specific examples. The second inorganic filler can be used alone or in combination of two or more kinds.

[0078] 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 further 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 can exhibit a leakage reduction effect and has excellent fluidity can be obtained.

[0079] As the second inorganic filler, an inorganic filler whose particle surface has been pretreated with an organic group can also be used. By pretreating the particle surface with an organic group, the adhesion to a semiconductor chip, an organic substrate, etc. is improved, which is preferable in terms of improving the toughness of the cured product of the sealing resin composition.

[0080] Whether the inorganic filler contains both the first inorganic filler and the second inorganic filler can be confirmed, for example, by obtaining the particle size distribution (frequency distribution) based on the volume of the inorganic filler. Specifically, in the frequency distribution based on the volume of the inorganic filler, when peaks exist in the ranges of 0.1 μm to 20 μm and 10 nm to 80 nm, respectively, it can be said that the inorganic filler contains both the first inorganic filler and the second inorganic filler. It should be noted that the confirmation method is not limited to the above method.

[0081] In addition, as a method for obtaining the proportion of the first or second inorganic filler in the inorganic filler, there is no particular limitation. For example, it can be obtained as follows: obtain the particle size distribution (frequency distribution) based on the volume of the inorganic filler, separate the two between the valleys of the peak corresponding to the first inorganic filler and the peak corresponding to the second inorganic filler, and divide the volume of the particles contained in each separated range by the total volume of the inorganic filler to obtain it. When the composition of the sealing resin composition is clear, the proportion of the first or second inorganic filler in the inorganic filler can be obtained from the composition of the sealing resin composition. It should be noted that the calculation method is not limited to the above method.

[0082] The value obtained by multiplying the specific surface area of the inorganic filler by the proportion of the mass of the inorganic filler in the mass of the solid components is 4 m 2 / g or more, preferably 4 m 2 / g to 30 m 2 / g, more preferably 5 m 2 / g to 26 m 2 / g, even more preferably 6 m 2 / g to 24 m 2 / g. When the value obtained by multiplying the specific surface area of the inorganic filler by the proportion of the mass of the inorganic filler in the mass of the solid components is within the above range, a resin composition that can exhibit a leakage reduction effect and has excellent fluidity can be obtained.

[0083] 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 other inorganic fillers are used in combination with the first inorganic filler and the second inorganic filler as the inorganic filler, the specific surface area of the inorganic filler refers to the weighted average of the first inorganic filler, the second inorganic filler, and other inorganic fillers.

[0084] In addition, the "mass of the solid components" refers to the mass of the solid components contained in the resin composition for sealing, and refers to the remaining components after removing volatile components such as organic solvents from the resin composition for sealing.

[0085] - Rubber additive -

[0086] From the viewpoint of alleviating the stress of the cured product of the resin composition for sealing, it is preferable that the resin composition for sealing contains a rubber additive as component (D). Examples of the rubber additive include acrylic rubber, urethane rubber, silicone rubber, butadiene rubber, etc. As the rubber additive, a rubber additive that is solid at normal temperature (25°C) can be used. The form is not particularly limited, and a particulate or pelletized rubber additive can be used. When the rubber additive is particulate, for example, the average particle size is preferably 0.01 μm to 20 μm, more preferably 0.02 μm to 10 μm, and even more preferably 0.03 μm to 5 μm.

[0087] As the rubber additive, a rubber additive that is liquid at normal temperature (25°C) can also be used. Examples of the liquid rubber additive include polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, polypropylene oxide, polydiorganosiloxane, etc.

[0088] In the case where the rubber additive is solid at room temperature (25°C), it is preferably heated and dissolved in an epoxy resin or a specific curing agent before use. Additionally, as the rubber additive, a rubber additive having a group reactive with an epoxy group at its terminal can be used. Regarding the rubber additive having a group reactive with an epoxy group at its terminal, it can be in any form that is solid or liquid at room temperature (25°C).

[0089] As the rubber additive, commercially available products can be used. Specific examples of commercially available products of the rubber additive include: CTBN1300, ATBN1300 - 16, CTBN1008 - SP, etc. manufactured by Ube Industries, Ltd.; silicone rubber powder (product name: AY42 - 119, etc.) manufactured by TORAY DOWCORNING Co., Ltd.; rubber powder (product name: XER81, etc.) manufactured by JSR Corporation, etc. The rubber additive is not limited to these specific examples. Additionally, the rubber additive can be used alone or in combination of two or more kinds.

[0090] -Coupling agent-

[0091] The sealing resin composition may contain a coupling agent as the (E) component. When the sealing resin composition contains a coupling agent, it is preferable from the viewpoint of the adhesiveness of the sealing resin composition.

[0092] The coupling agent is not particularly limited and can be appropriately selected and used from known coupling agents. Examples include: silane compounds such as aminosilane, epoxy silane, mercapto silane, alkyl silane, ureido silane, vinyl silane having at least one selected from primary amino group, secondary amino group and tertiary amino group; titanate compounds, etc. Among these, from the viewpoint of the adhesiveness of the sealing resin composition, epoxy silane compounds are preferred.

[0093] As the coupling agent, commercially available products can be used. Specific examples of commercially available products of the coupling agent include KBM - 403, KBE - 903, KBE - 9103, etc. manufactured by Shin-Etsu Chemical Co., Ltd. The coupling agent is not limited to these specific examples. The coupling agent can be used alone or in combination of two or more kinds.

[0094] -Other components-

[0095] In the sealing resin composition, within the range not impairing the object of the present disclosure, other components such as a thixotropic agent for improving workability, pigments such as carbon black, dyes, ion trappers, defoaming agents, leveling agents, antioxidants, reactive diluents, organic solvents, etc. can be further contained as needed.

[0096] The resin composition for sealing can be obtained, for example, by stirring, melting, mixing, dispersing, etc. epoxy resin, a specific curing agent, an inorganic filler, and other components used as required, either all at once or separately, while performing heat treatment as required. Particularly when the specific curing agent is in a solid state, if the specific curing agent is incorporated in a solid state, the viscosity sometimes increases and the workability deteriorates. Therefore, it is preferred to use the specific curing agent after liquefying it by preheating. The device for mixing, stirring, dispersing, etc. of these components is not particularly limited, and examples include a kneader, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. equipped with a stirring device, a heating device, etc. By mixing and kneading the above components using these devices and defoaming as required, the resin composition for sealing can be obtained.

[0097] There is no particular limitation on the viscosity of the resin composition for sealing. Among them, from the viewpoint of high fluidity, it is preferably 0.1 Pa·s to 50.0 Pa·s at 25°C, more preferably 0.1 Pa·s to 20.0 Pa·s, and further preferably 0.1 Pa·s to 10.0 Pa·s. It should be noted that the viscosity of the resin composition for sealing is measured at 25°C using an E-type viscometer (cone angle 3°, rotation speed 10 revolutions per minute).

[0098] In addition, when the resin composition for sealing is used for applications such as underfill materials, as an index of the ease of filling the resin composition for sealing into a narrow gap of several tens of μm to several hundreds of μm around 100°C to 120°C, the viscosity at 110°C is preferably 0.20 Pa·s or less, more preferably 0.15 Pa·s or less. It should be noted that the viscosity of the resin composition for sealing at 110°C can be measured using a rheometer AR2000 (manufactured by TA Instrument, aluminum cone 40 mm, shear rate 32.5 / second).

[0099] In addition, for the resin composition for sealing, the ratio of the viscosity at a rotation speed of 1.5 revolutions per minute to the viscosity at a rotation speed of 10 revolutions per minute, that is, the thixotropic index [(viscosity at 1.5 revolutions per minute) / (viscosity at 10 revolutions per minute)], measured at 25°C using an E-type viscometer is preferably 0.5 to 1.5, more preferably 0.8 to 1.2. When the thixotropic index is in the above range, the fillet formation property in the underfill material application is further improved. It should be noted that the viscosity and thixotropic index of the resin composition for sealing can be set within a desired range by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, etc.

[0100] The curing conditions of the resin composition for sealing are not particularly limited, and it is preferably heated at 80°C to 165°C for 1 minute to 150 minutes.

[0101] <Electronic component device>

[0102] 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 disposed in the gap between the substrate and the electronic component. The electronic component device of the present disclosure can be obtained by sealing an electronic component with the sealing resin composition of the present disclosure. By using the sealing resin composition to seal the electronic component, the electronic component device of the present disclosure has excellent temperature cycle resistance.

[0103] Examples of the electronic component device include: an electronic component device obtained by mounting active components such as semiconductor chips, transistors, diodes, thyristors, and passive components such as capacitors, resistors, resistor arrays, coils, switches, etc. on a substrate having a circuit layer such as a lead frame, a completed wiring tape carrier, a rigid wiring board, a flexible wiring board, glass, a silicon wafer, etc., and sealing necessary parts with the sealing resin composition of the present disclosure.

[0104] As one of the objects to which the present disclosure can be applied, in particular, a semiconductor device obtained by flip-chip bonding a semiconductor element using bump connections on a wiring formed on a rigid wiring board, a flexible wiring board, or glass can be cited. As specific examples, electronic component devices such as flip-chip BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film) can be cited.

[0105] The sealing resin composition of the present disclosure is suitable as an underfill material for flip chips with excellent reliability. As a flip-chip field where the sealing resin composition of the present disclosure is particularly suitable for application, there are components such as flip-chip semiconductor components in which the bump material connecting the wiring substrate and the semiconductor element does not use a conventional lead-containing solder but uses a lead-free solder such as Sn-Ag-Cu. For a flip chip obtained by bump connection using a lead-free solder that is brittle compared to conventional lead solders in terms of physical properties, the sealing resin composition of the present disclosure can also maintain good reliability. In addition, when mounting a chip-level package such as a wafer-level CSP on a substrate, the reliability can be improved by applying the sealing resin composition of the present disclosure.

[0106] <Method for manufacturing an electronic component device>

[0107] The method for manufacturing an electronic component device of the present disclosure includes a step of sealing a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer with the sealing resin composition of the present disclosure.

[0108] The process of sealing a substrate having a circuit layer and an electronic component with the sealing resin composition of the present disclosure is not particularly limited. Examples include: a post-injection method in which, after connecting an electronic component and a substrate having a circuit layer, a sealing resin composition is applied to the gap between the electronic component and the substrate by capillary action, and then a curing reaction of the sealing resin composition is carried out; and a pre-coating method in which the surface of at least one of the substrate having a circuit layer and the electronic component is first applied with the sealing resin composition of the present disclosure, and when the electronic component is connected to the substrate by thermocompression bonding, the connection between the electronic component and the substrate and the curing reaction of the sealing resin composition are carried out at once.

[0109] As a method for applying the sealing resin composition, casting methods, dispensing methods, printing methods, etc. can be cited.

[0110] By using the sealing resin composition of the present disclosure, an electronic component device such as a flip chip mounting body with suppressed leakage can be easily manufactured.

[0111] Examples

[0112] The present invention will be described below based on examples, but the present invention is not limited by the following examples. It should be noted that in the following examples, parts and % represent parts by mass and mass %, respectively, unless otherwise specified.

[0113] Each component was blended so as to have the compositions shown in Tables 1 and 2, and kneaded and dispersed using a three-roll mill and a vacuum kneader to prepare the sealing resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7. It should be noted that the blending unit in the table is parts by mass, and "-" indicates "not blended". In addition, the content (% by mass) of the inorganic filler in the sealing resin composition was calculated from the blending amounts of the respective components.

[0114] (Examples 1 to 9, Comparative Examples 1 to 7)

[0115] As epoxy resins, a bisphenol F type epoxy resin (Epoxy resin 1; manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "YDF-8170C", epoxy equivalent: 160 g / eq) and a trifunctional amine type epoxy resin having an epoxy group (Epoxy resin 2; manufactured by Mitsubishi Chemical Corporation, trade name "jER630", epoxy equivalent: 95 g / eq) were prepared.

[0116] As specific curing agents, a diaminotoluene type amine curing agent (Amine curing agent 1; manufactured by Mitsubishi Chemical Corporation, trade name "jER cureW") and a diaminodiphenylmethane type amine curing agent (Amine curing agent 2; manufactured by Nippon Kayaku Co., Ltd., trade name "Kayahard-AA") were prepared.

[0117] As an inorganic filler, an inorganic filler with an average particle diameter of 0.5 μm and a specific surface area of 4.5 m 2 / g (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 m 2 / g (inorganic filler 2: manufactured by Admatechs Co., Ltd., trade name "YA050C - SZ2), an 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"), an inorganic filler with an average particle diameter of 0.3 μm and a specific surface area of 14 m 2 / g (inorganic filler 4: manufactured by Admatechs Co., Ltd., trade name "SE1050"), an inorganic filler with an average particle diameter of 0.3 μm and a specific surface area of 15 m 2 / g (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 6: manufactured by Admatechs Co., Ltd., trade name "SE1030 - SET"), an inorganic filler with an average particle diameter of 0.15 μm and a specific surface area of 30 m 2 / g (inorganic filler 7: manufactured by 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").

[0118] Regarding the resin composition for sealing obtained above, the evaluation of each property was carried out as described below. In addition, the respective numerical values are shown in Tables 1 and 2 below.

[0119] (1) Fluidity: Viscosity and thixotropic index

[0120] The viscosity (room temperature viscosity, Pa·s) of the resin composition for sealing at 25 °C was measured using an E-type viscometer (cone angle 3°, rotation speed 10 revolutions per minute). In addition, the thixotropic index at 25 °C was set as the ratio of the viscosity at a rotation speed of 1.5 revolutions per minute to the viscosity at a rotation speed of 10 revolutions per minute [(viscosity at 1.5 revolutions per minute) / (viscosity at 10 revolutions per minute)]. The viscosity (Pa·s) at 110 °C was measured using a rheometer AR2000 (aluminum cone 40 mm, shear rate 32.5 / second).

[0121] (2) Heat resistance: Glass transition temperature (Tg), coefficient of thermal expansion (CTE)

[0122] For a test piece (φ4 mm × 20 mm) prepared by curing the sealing resin composition under the conditions of 165°C for 2 hours, measurement was carried out using a thermomechanical analysis device (manufactured by TA Instrument Japan Co., Ltd., trade name TMA Q400) under the conditions of a load of 15 g, a measurement temperature range of -50°C to 220°C, and a heating rate of 5°C / minute.

[0123] In addition, the coefficient of thermal expansion in the temperature range below Tg is designated as CTE1, and the coefficient of thermal expansion in the temperature range above Tg is designated as CTE2. Tg and CTE represent thermal stability. Tg is preferably around 100°C to 130°C, and the lower CTE1 and CTE2 are, the more preferable.

[0124] (3) Leakage: Measurement of leakage length

[0125] The solder resist substrate was subjected to Ar2 plasma treatment (400 W, 2 minutes), and 30 mg of the sealing resin composition filled in a syringe was discharged onto the solder resist substrate subjected to Ar2 plasma treatment with a 20G needle for potting, and then cured at 150°C for 120 minutes. After curing, the leakage length was measured using an optical microscope. As the substrate, a substrate having a solder resist (PSR - 4000 - AUS703 manufactured by Taiyo Ink Manufacturing Co., Ltd.) formed on FR - 4 (manufactured by Hitachi Chemical Co., Ltd., MRC - E - 679) was used. The leakage length is preferably 500 μm or less, more preferably 400 μm or less, and further preferably 350 μm or less.

[0126]

[0127]

[0128] In Tables 1 and 2, the "content ratio of the second inorganic filler" refers to the proportion of the second inorganic filler in the inorganic filler.

[0129] In Tables 1 and 2, the "specific surface area × proportion of inorganic filler" refers to "the value obtained by multiplying the specific surface area of the inorganic filler by the proportion of the mass of the inorganic filler in the mass of the solid components".

[0130] From the results of Tables 1 and 2, it can be seen that the sealing resin compositions of Examples 1 to 9 are superior in leakage compared to the sealing resin compositions of Comparative Examples 1 to 7.

[0131] All documents, patent applications, and technical standards cited in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and separately indicated to be incorporated by reference.

Claims

1. A resin composition for sealing, which comprises (A) an epoxy resin, (B) a curing agent having at least 1 amino group in 1 molecule, and (C) an inorganic filler, The (C) inorganic filler comprises (C1) a first inorganic filler having an average particle size of 0.3 μm to 5 μm and (C2) a second inorganic filler having an average particle size of 10 nm to 80 nm, The value obtained by multiplying the specific surface area of the inorganic filler (C) by the proportion of the mass of the inorganic filler (C) in the mass of the solid components is 4.0 m 2 / g or more.

2. The resin composition for sealing according to claim 1, wherein The viscosity at 110 °C is 0.20 Pa·s or less.

3. The resin composition for sealing according to claim 1 or claim 2, wherein The proportion of the (C2) second inorganic filler having an average particle size of 10 nm to 80 nm in the (C) inorganic filler is 0.3 mass% or more.

4. The resin composition for sealing according to any one of claims 1 to 3, wherein, The proportion of the (C2) second inorganic filler having an average particle size of 10 nm to 80 nm in the (C) inorganic filler is 30 mass% or less.

5. The resin composition for sealing according to any one of claims 1 to 4, wherein, The proportion of the (C1) first inorganic filler having an average particle size of 0.3 μm to 5 μm in the (C) inorganic filler is 70 mass% or more.

6. The resin composition for sealing according to any one of claims 1 to 5, wherein, The viscosity at 25 °C is 0.1 Pa·s to 50.0 Pa·s.

7. The resin composition for sealing according to any one of claims 1 to 6, wherein, The (C1) first inorganic filler having an average particle size of 0.3 μm to 5 μm contains silica.

8. The resin composition for sealing according to any one of claims 1 to 7, wherein, The (C2) second inorganic filler having an average particle size of 10 nm to 80 nm contains silica.

9. The resin composition for sealing according to any one of claims 1 to 8, wherein, The content rate of the (C) inorganic filler is 40 mass% to 85 mass%.

10. The resin composition for sealing according to any one of claims 1 to 9, wherein, The specific surface area of the first inorganic filler (C1) having an average particle diameter of 0.3 μm to 5 μm is 1 m 2 / g to 30 m 2 / g.

11. The resin composition for sealing according to any one of claims 1 to 10, wherein, The specific surface area of the second inorganic filler (C2) with an average particle size of 10 nm to 80 nm is 20 m 2 / g to 500 m 2 / g.

12. The resin composition for sealing according to any one of claims 1 to 11, wherein, The thixotropic index at 25 °C is 0.5 to 1.

5.

13. An electronic component device, which comprises: A substrate having a circuit layer; An electronic component disposed on the substrate and electrically connected to the circuit layer; and A cured product of the resin composition for sealing according to any one of claims 1 to 12 disposed in the gap between the substrate and the electronic component.

14. A method for manufacturing an electronic component device, which has a step of sealing a substrate having a circuit layer and an electronic component disposed on the substrate and electrically connected to the circuit layer with the resin composition for sealing according to any one of claims 1 to 12.

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