JP2015083634A - Epoxy resin, electronic component device using the epoxy resin and method for manufacturing electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin which can adjust a curing time and can reduce generation of voids when used as a sealing material for an electronic component device and to provide an electronic component device capable of adjusting a curing time and reducing generation of voids and a method for manufacturing the electronic component device.SOLUTION: There is provided an epoxy resin composition which comprises (A) an epoxy resin, (B) a six-membered ring lactone having an aromatic skeleton, (C) a curing accelerator and (D) an inorganic filler having an average particle diameter of 0.1 to 10 μm. Further, there is provided an epoxy resin composition which comprises (A) an epoxy resin, (B) a six-membered ring lactone having an aromatic skeleton, (C) a curing accelerator and (D) an inorganic filler and has an inorganic filler in which the particle size distribution has a peak between 0.1 to 10 μm as the (D) inorganic filler.

Description

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

  Conventionally, in the field of element sealing of electronic component devices such as transistors, ICs (Integrated Circuits), and LSIs (Large Scale Integrations), sealing is performed using a sealing material including a resin in terms of productivity and cost. The technique to do is becoming mainstream. As a sealing material, an epoxy resin composition is widely used. This is because the epoxy resin is balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts.

  In electronic component devices mounted with bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package), epoxy resin compositions that are liquid at room temperature are widely used as sealing materials. . Also, in an electronic component device (flip chip) in which electronic components are bump-connected on a wiring board made of ceramic, glass epoxy resin, glass imide resin, polyimide film or the like, a gap between the bump-connected electronic component and the wiring board is used. As an underfill material filling (gap), an epoxy resin composition that is liquid at room temperature is used. In bare chip mounting, the circuit forming surface is not sufficiently protected, so moisture and ionic impurities can easily enter.In flip chip mounting, the electronic component and the wiring board may have different coefficients of thermal expansion, so the connection part Thermal stress may occur. Therefore, the epoxy resin composition plays an important role in protecting electronic components from temperature and humidity and mechanical external force.

  As the filling method of the underfill material, after connecting the electronic component and the wiring board, a post-filling method in which the underfill material is infiltrated into the gap between the electronic component and the wiring board using a capillary phenomenon, and an underfill material is used. There is a prior application method in which the connection between the electronic component and the wiring substrate and the curing reaction of the underfill material are performed collectively when the electronic component is first applied onto the wiring substrate and thermocompression bonded to connect the electronic component to the wiring substrate. Generally, the last-in method is excellent in quality and reliability, and the pre-coating method has a feature that the number of steps can be reduced.

  As the underfill material used in the pre-coating method, if the curability is low, the time for thermocompression bonding becomes long and the workability is lowered. As a method for enabling the epoxy resin composition to be cured for a short time, a method using an imidazole compound as a curing accelerator (see, for example, Patent Document 1), and a coating with a thermosetting resin around the imidazole compound as a curing accelerator. A method using at least one of fine sphere particles and amine adduct particles obtained by coating with (see, for example, Patent Document 2) has been reported.

Japanese Patent Publication No. 7-53794 Japanese Patent No. 3446730

The underfill material reported in the above-mentioned patent document realizes curing in a short time in order to improve workability. These are applied to CSP (Chip Size Package) which is a small chip size package. Since the chip thickness of CSP is thin, heat transfer is good at the time of thermocompression bonding and it can be cured in a short time. However, for FC-BGA (Flip Chip-Ball Grid Array) which is a package with a large chip size, etc. When a conventional epoxy resin composition is used as an underfill material of a pre-coating method, the chip thickness increases, so that heat transfer is slow, and a longer time is required for curing than CSP. Moreover, since time is required for thermocompression bonding, voids are easily generated, and the connectivity and reliability are insufficient.
Therefore, an underfill material that can be applied to a pre-coating method and can sufficiently reduce the generation of voids even when the curing time is long is required, but it has not been obtained yet.

  The present invention has been made in view of such circumstances, and it is possible to reduce the generation of voids even when the curing time is long, and to improve the reliability of an electrical component device and electrical connection with excellent electrical connection reliability. An object of the present invention is to provide a method for manufacturing an electronic component device having excellent voids.

The present invention relates to the following.
<1> An epoxy containing (A) an epoxy resin, (B) a 6-membered ring lactone having an aromatic skeleton, (C) a curing accelerator, and (D) an inorganic filler having an average particle size of 0.1 to 10 μm. Resin composition.
<2> (A) an epoxy resin, (B) a 6-membered ring lactone having an aromatic skeleton, (C) a curing accelerator, (D) an inorganic filler, and the (D) inorganic filler has a particle size distribution. The epoxy resin composition which has an inorganic filler which has a peak between 0.1-10 micrometers.
<3> The epoxy resin composition according to <1> or <2>, wherein the aromatic skeleton of (B) is a benzene ring or a naphthalene ring.
<4> The 6-membered ring lactone of (B) is condensed to a benzene ring or a naphthalene ring as an aromatic skeleton, and is represented by the following general formula (1) or (2), <1> to <3> The epoxy resin composition as described in any one of these.

（式中のＲ_１〜Ｒ_１４は、それぞれ同一であっても異なっていてもよい。Ｒ_１〜Ｒ_１４は、水素原子、水酸基、または炭素原子数が１〜２０であり、直鎖もしくは分岐のあるアルキル基、または芳香族もしくはヘテロ芳香族骨格または６員環ラクトン骨格に直接結合しているか、または架橋原子もしくは架橋基によって該骨格に結合しており、好ましくは炭素原子数が６〜２０である、アリール、アルカリールまたはアラルキル基、および／または隣接基Ｒ_５およびＲ_６、またはＲ_６およびＲ_７、Ｒ_７およびＲ_８、Ｒ_９およびＲ_１０、Ｒ_１１およびＲ_１２、Ｒ_１２およびＲ_１３、またはＲ_１３およびＲ_１４は、６員環ラクトン骨格を形成し、および／または、Ｒ_５〜Ｒ_８、およびＲ_９〜Ｒ_１４のいずれかは、一般式（Ｉ）または（ＩＩ）で示される第２のラクトンへの脂肪族、脂環式または芳香族の「架橋基」である。）
＜５＞＜１＞〜＜４＞のいずれか１項に記載のエポキシ樹脂組成物を用いて封止される電子部品装置。
＜６＞電子部品と配線基板とを金属バンプを介して接合することで電子部品装置を製造する電子部品装置の製造方法であって、前記電子部品の前記配線基板と対向する側の面及び前記配線基板の前記電子部品と対向する側の面の少なくとも一方に請求項１〜請求項４のいずれか１項に記載のエポキシ樹脂組成物を付着させる付着工程と、前記電子部品と前記配線基板とを前記金属バンプを介して加圧しながら対向させることで、前記電子部品と前記配線基板との間隙に前記エポキシ樹脂組成物を充填させ、かつ、前記電子部品と前記配線基板とを前記金属バンプを介して接触させる加圧工程と、前記加圧工程中及び前記加圧工程後の少なくとも一方で、前記電子部品と前記配線基板とを前記金属バンプを介して加圧して接触する状態で熱処理して前記電子部品と前記配線基板とを前記金属バンプを介して接合させ、かつ、前記エポキシ樹脂組成物を硬化する熱処理工程とを有する電子部品装置の製造方法。

(In the formula, R _{1 to} R ₁₄ may be the same or different. R _{1 to} R ₁₄ have a hydrogen atom, a hydroxyl group, or a carbon atom number of 1 to 20, and are linear or branched. Or an aromatic or heteroaromatic skeleton or a 6-membered lactone skeleton, or is bonded to the skeleton by a bridging atom or bridging group, preferably having 6 to 20 carbon atoms. An aryl, alkaryl or aralkyl group, and / or adjacent groups R ₅ and R ₆ , or R ₆ and R ₇ , R ₇ and R ₈ , R ₉ and R ₁₀ , R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ or _{R 13} and _{R 14,} may form a 6-membered ring lactone skeleton, and / _or, any of R 5 to R _8, and _R 9 _{to R 14,} the general formula ( ) Or (aliphatic to a second lactone represented by II), a "bridging group" alicyclic or aromatic.)
<5> An electronic component device that is sealed using the epoxy resin composition according to any one of <1> to <4>.
<6> An electronic component device manufacturing method for manufacturing an electronic component device by joining an electronic component and a wiring board via metal bumps, the surface of the electronic component facing the wiring substrate, and the surface The adhesion process which makes the epoxy resin composition of any one of Claims 1-4 adhere to at least one of the surface of the wiring board facing the said electronic component, The said electronic component, the said wiring board, Is made to oppose while being pressed through the metal bump, so that the gap between the electronic component and the wiring substrate is filled with the epoxy resin composition, and the electronic component and the wiring substrate are attached to the metal bump. A heat treatment in a state in which the electronic component and the wiring board are in pressure contact with each other through the metal bumps, and at least one of during and after the pressurization process. Said electronic component and the wiring substrate are joined via the metal bump, and a method of manufacturing an electronic component device and a heat treatment step of curing the epoxy resin composition Te.

  When the epoxy resin composition capable of adjusting the gelation time of the present invention is used as a material for an electronic component device, it is possible to provide an electronic component device that is excellent in the connectivity of the electronic component device and has few voids.

It is a figure explaining the process of the manufacturing method of the electronic component apparatus by a prior application system. It shows a ¹ H-NMR chart of OH-DHC used in Examples.

Hereinafter, the present invention will be described in detail.
In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the present specification, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. To do.

  Hereinafter, the epoxy resin composition, the electronic component device, and the method for producing the electronic component device of the present invention will be described in detail.

<Epoxy resin composition>
The epoxy resin composition of the present invention contains an epoxy resin, a 6-membered ring lactone having an aromatic skeleton, a curing accelerator, and an inorganic filler having an average particle size of 0.1 to 10 μm.

The epoxy resin composition of the present invention is preferably liquid at room temperature. If the epoxy resin composition is liquid at room temperature, the epoxy resin composition of the present invention can be easily handled when used as an underfill material for electronic component devices.
In this specification, “room temperature” means 25 ° C. In this specification, “liquid at room temperature” means a state in which fluidity is exhibited at 25 ° C. Further, in the present specification, “liquid” means a substance that exhibits fluidity and viscosity and has a viscosity of 0.0001 to 1000 Pa · s at 25 ° C. as a measure of viscosity. In the present specification, the “viscosity” is defined as a viscosity when an epoxy resin composition maintained at 25 ° C. is measured with a rheometer at a shear rate of 5.0 s ⁻¹ . Specifically, the “viscosity” is measured as a shear viscosity at a temperature of 25 ° C. using a rotary shear viscometer equipped with a cone plate (diameter 40 mm, cone angle 0 °).

By setting the epoxy resin composition of the present invention to the above configuration, the gelation time can be adjusted by the amount of the curing accelerator. Moreover, when used as a sealing material for an electronic component device, the reliability of electrical connection can be obtained, and the voids of the cured resin can be sufficiently reduced. The reason can be considered as follows.
That is, according to the knowledge obtained by the present inventors, the good voidless property required for the epoxy resin composition used in the manufacturing method of the electronic component device to which the pre-coating method is applied has six members used as a curing agent. This is achieved by using a ring lactone. The present inventors believe that this is because the generation of voids can be reduced by adding water that contributes to the cause of voids to the carbonyl group in the 6-membered ring lactone. It can be considered that the same phenomenon occurs in an acid anhydride having a skeleton similar to a 6-membered ring lactone to reduce the generation of voids. However, when an acid anhydride is used as the curing agent, the reactivity with the epoxy resin is high, so that it is difficult to adjust the gelation time even if the amount of the curing accelerator used is reduced. On the other hand, the 6-membered ring lactone, which has a lower reactivity with the epoxy resin than the acid anhydride, can adjust the gelation time depending on the amount of curing accelerator and the like, and can achieve the intended purpose. Yes.
Moreover, when an epoxy resin composition with a low viscosity is used, when an epoxy resin flows and interposes between an electronic component and a wiring board, it is guessed that it becomes difficult to generate an unfilled location and an entrainment void.

(A) Epoxy resin The epoxy resin usable in the present invention is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. As an epoxy resin in this invention, the epoxy resin generally used can be used in the underfill material used for the manufacture use of an electronic component apparatus. In addition, an epoxy resin that is liquid at room temperature may be used so that the underfill material of the present invention is liquid at room temperature, or an epoxy resin that is solid at room temperature and an epoxy resin that is liquid at room temperature may be used in combination. .

As epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like are obtained by reaction of epichlorohydrin with glycidyl ether type epoxy resins and orthocresol novolac type epoxy resins. A novolak type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or copolymerization of a compound and an aldehyde compound, a glycidyl ester type epoxy resin obtained by the reaction of a polybasic acid such as phthalic acid or dimer acid and epichlorohydrin, p -Glycidylamine type epoxy resin obtained by reaction of amine compounds such as aminophenol, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, and olefin bond. Linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing with a peracid such as an acid, and an epoxy resin having a resorcinol skeleton.
These epoxy resins may be used alone or in combination of two or more.

  Among them, a liquid epoxy resin at room temperature is preferable from the viewpoint of low viscosity, and from the viewpoint of reactivity and heat resistance, a glycidyl ether type epoxy resin having a bisphenol skeleton, a glycidyl ether type epoxy resin having a naphthalene skeleton, and glycidylamine. Type epoxy resin is preferred.

  The epoxy resin in the present invention is preferably a modified epoxy resin that is a reaction product of an epoxy resin and rubber particles. The modified epoxy resin can be obtained by reacting rubber particles having a functional group capable of reacting with an epoxy group and an epoxy group possessed by the epoxy resin. As the modified epoxy resin, for example, rubber particles having a reactive functional group such as a carboxy group, an amino group, and a hydroxyl group and an epoxy resin are preliminarily heated and melted to finely disperse the rubber particles, and the epoxy group and the reactive functional group can be dispersed. Examples thereof include modified epoxy resins obtained by reacting groups.

  Moreover, as an epoxy resin in this invention, if it is in the range with which the effect of this invention is achieved, a solid epoxy resin can also be used together at room temperature. From the viewpoint of fluidity, the content of the epoxy resin solid at room temperature used in combination is preferably 20% by mass or less based on the total amount of the epoxy resin.

  Furthermore, the purity of these epoxy resins, particularly the amount of hydrolyzable chlorine, is preferably less because it involves corrosion of aluminum wiring in ICs and the like. In order to obtain an underfill material excellent in moisture resistance, the amount of hydrolyzable chlorine is preferably 500 ppm or less in the total amount of the epoxy resin. Here, the hydrolyzable chlorine amount is a value determined by potentiometric titration after dissolving 1 g of the epoxy resin of the sample in 30 ml of dioxane, adding 5 ml of 1M-KOH methanol solution and heating to reflux for 30 minutes.

  The content of the total epoxy resin in the epoxy resin composition of the present invention is preferably 5 to 60% by mass and more preferably 7.5 to 55% by mass from the viewpoint of fluidity and cured property control. Preferably, it is 10-50 mass%, and it is still more preferable. Moreover, it is preferable that it is 40-95 mass% from a viewpoint of hardened | cured material property control, and, as for the content rate of the modified epoxy resin which occupies in all the epoxy resins, it is more preferable that it is 45-93 mass%, and is 50-90 mass%. More preferably it is.

The epoxy equivalent of the epoxy resin contained in the epoxy resin composition of the present invention is preferably 50 to 300 g / eq, more preferably 60 to 250 g / eq, and still more preferably 70 to 200 g / eq.
The epoxy equivalent is measured by dissolving a weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and a tetraethylammonium bromide acetic acid solution, and then performing potentiometric titration with a perchloric acid acetic acid standard solution. An indicator may be used during the titration.

(B) 6-membered ring lactone having an aromatic skeleton The epoxy resin composition of the present invention contains a 6-membered ring lactone having an aromatic skeleton. By using a 6-membered ring lactone having an aromatic skeleton, generation of voids can be reduced even when the curing time is long. 6-membered ring lactones having an aromatic skeleton are one or more straight or branched chains containing 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, most preferably 1 to 6 carbon atoms. It may be further substituted with an alkyl group (for example, a methyl, ethyl or propyl group). Further substituents can be selected from hydroxy, aryl, acrylaryl, or aralkyl groups (preferably containing 6-20 carbon atoms), which are directly attached to the aromatic or 6-membered lactone skeleton Or bonded to the skeleton by a bridging atom or bridging group (such as —O—, —S—, — (CO) —, —O— (CO) — or — (CO) —O—). You can also Six-membered ring lactones having an aromatic skeleton may be used alone or in combination of two or more.

  Further, the 6-membered lactone skeleton is condensed with the adjacent carbon atom of the aromatic skeleton to form a bifunctional lactone, for example, a bifunctional lactone represented by the following general formula (3) (Max. JN, et al., J. Heterocyclic Chem., 12 (22), 417 (1975)).

  Examples of the 6-membered aromatic skeleton condensed to the 6-membered lactone skeleton include, for example, a benzene skeleton, a naphthalene skeleton, or a pyridine skeleton. Particularly preferred is a benzene skeleton or a naphthalene skeleton from the viewpoint of storage stability when mixed with an epoxy resin.

The 6-membered lactone is preferably condensed with a benzene ring or a naphthalene ring as an aromatic skeleton from the viewpoint of storage stability when mixed with an epoxy resin, and from the viewpoint of reactivity with the epoxy resin, A structure represented by the general formula (1) or (2) shown is more preferable. Especially, it is especially preferable that it is a compound represented by General formula (1) from a viewpoint of the viscosity at the time of mixing with an epoxy resin.
An example of the case where R ₂ is an aliphatic, alicyclic or aromatic “crosslinking group” to the second lactone represented by the general formula (1) is represented by the following formula (4).

  Examples of the crosslinking group include an alkylene group, a phenylene group, an -O-alkylene-O- group, an -O-phenylene-O- group, an -O-CO-alkylene-CO-O- group, and an -O-CO-phenylene-CO. Examples include —O— group, —O—CO—NH-alkylene-NH—CO—O— group, —O—CO—NH-phenylene-NH—CO—O— group, and the like. The alkylene group or phenylene group may have a substituent, and the substituent is preferably an alkyl group containing 1 to 4 carbon atoms.

The 6-membered lactone is preferably dihydrocoumarin (R _{1 to} R _{8 in} the general formula (1) are hydrogen atoms) or substituted dihydrocoumarin. In the substituted dihydrocoumarin, R _{1 to} R ₄ in the general formula (1) are hydrogen atoms, and R _{5 to} R ₈ may be the same or different, and may be a hydrogen atom, a hydroxyl group, or a carbon atom. The number is 1 to 20, preferably 1 to 12, more preferably 1 to 6, and is directly bonded to a linear or branched alkyl group or aromatic, or to the skeleton by a bridging atom or bridging group Aryl, alkaryl or aralkyl groups, and / or adjacent groups R ₅ and R ₆ , or R ₆ and R ₇ , or R ₇ and R ₈ , preferably having 6 to 20 carbon atoms Forms a 6-membered lactone skeleton and / or any of R _{5 to} R ₈ is an aliphatic, cycloaliphatic or aromatic “bridge” to a second lactone of the general formula (1) In "base" Is a compound that satisfies the Rukoto.

  Examples of specific structural formulas corresponding to general formula (1) or (2) are shown below.

The 6-membered ring lactone condensed to the aromatic skeleton preferably contains an amount such that the active hydrogen group is in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the component (A), more preferably It is to contain an amount in the range of 0.5 to 1.0 equivalent. Here, the active hydrogen group means a functional group capable of reacting with an epoxy group, and when the active hydrogen group is less than 0.5 equivalent, the generated void may not be sufficiently suppressed. Moreover, when it exceeds 1.0 equivalent of active hydrogen groups greatly, considerable time is required until it hardens | cures, and workability | operativity may deteriorate.
Moreover, as long as the effect of the present invention is not lost, an epoxy resin and a curing agent capable of curing reaction may be used in combination. If the hardening | curing agent used together is a hardening | curing agent generally used for the epoxy resin composition for electronic components, there will be no restriction | limiting in particular.

(C) Curing accelerator The curing accelerator used in the present invention is not particularly limited, and is a urea compound, a tertiary amine and a salt thereof, an imidazole and a salt thereof, a phosphorus curing accelerator, a carboxylic acid metal salt. Alternatively, one or more of Lewis acids, Bronsted acids and their salts can be selected and used. Among these, it is more preferable to use imidazole and a salt thereof from the viewpoints of storage stability, curing acceleration ability, and the like.

  A thermoplastic resin can be added to the epoxy resin composition of the present invention as long as the effects of the present invention are not lost. Examples of the thermoplastic resin include phenoxy resin, polyimide resin, polyamide resin, polycarbodiimide resin, cyanate ester resin, acrylic resin, polyester resin, polyethylene resin, polyethersulfone resin, polyetherimide resin, polyvinyl acetal resin, urethane. Resins, acrylic rubber and rubber particles are preferred. Among these, from the viewpoint of excellent heat resistance, phenoxy resin, polyimide resin, acrylic rubber, rubber particles, acrylic resin, cyanate ester resin, and polycarbodiimide resin are more preferable, and further, versatility, adjustment of molecular weight and property provision, etc. From the standpoint of being easy (such as during synthesis), phenoxy resin, polyimide resin, rubber particles, acrylic rubber, and acrylic resin are more preferable. These components can be used alone or as a mixture or copolymer of two or more.

(D) Inorganic filler The epoxy resin composition of this invention mix | blends an inorganic filler. In the present invention, the inorganic filler is not particularly limited as long as it is an inorganic particle generally used in an epoxy resin composition for electronic parts. As an inorganic filler, a metal oxide, a metal, a mineral, etc. are mentioned, This may be used individually by 1 type and may use 2 or more types together. The inorganic particles are used for improving the function and imparting functions of the obtained cured product, and specifically include surface hardness, heat resistance, conductivity, antistatic properties, toughness, impact resistance, low thermal expansion, and the like. As metal oxides, silicon oxide, titanium oxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, indium oxide, aluminum oxide, antimony oxide, oxidation Examples include cerium, magnesium oxide, iron oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide, and fluorine-doped tin oxide. Examples of the metal include gold, silver, copper, aluminum, nickel, iron, zinc, and stainless steel. Examples of the mineral include minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, verculite, and sericite. In addition, carbon black, acetylene black, ketjen black, carbon compounds such as carbon nanotubes, metal hydroxides such as aluminum hydroxide and magnesium oxide, fillers such as glass such as glass beads, glass flakes, and glass balloons. Can be mentioned. In addition, as the inorganic filler, powder may be used as it is, or those dispersed in a resin may be used. Among the inorganic fillers, fused silica is preferable, and spherical silica is more preferable from the viewpoint of fluidity and penetration into the fine gaps. Further, these inorganic fillers may be those whose surfaces are treated with a coupling agent as required.

In the present invention, that the silica is spherical means that the sphericity satisfies the condition of 0.7 or more. As a method for measuring the sphericity, for example, image processing is performed with an electron microscope, and from the observed particle area and perimeter, (sphericity) = {4π × (area) ÷ (perimeter) ² } The calculated value was used.

  As coupling agents for treating the surface of inorganic fillers, known silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, titanium compounds, aluminum chelate compounds, aluminum zirconium compounds, etc. Of coupling agents. Among these, it is preferable to use alkylsilane as a coupling agent.

  The average particle diameter of the inorganic filler used in the present invention is not particularly limited as long as the effect of the present invention is achieved, and is preferably 0.1 to 10 μm, preferably 0.15 to 5 μm. Is more preferable, and 0.2 to 1 μm or less is further preferable. If the average particle size of the inorganic particles is 10 μm or less, the penetration of the epoxy resin composition into the fine gaps and the fluidity are improved, and there is a tendency that generation of voids and unfilling of the epoxy resin composition are less likely to occur. is there. Furthermore, the inorganic filler is less likely to bite into the connection part between the electronic component and the wiring board, and connection failure tends to be less likely to occur. Moreover, when the average particle diameter of the inorganic particles is 0.1 μm or more, there is a tendency that the viscosity does not increase greatly.

  The maximum particle size of the inorganic filler used in the present invention is not particularly limited as long as the effect of the present invention is achieved, but is preferably 40 μm or less, more preferably 30 μm or less, and 20 μm. More preferably, it is as follows. If the maximum particle size of the inorganic filler is 20 μm or less, the penetration property and fluidity of the epoxy resin composition into the fine gap are improved, and there is a tendency that generation of voids and unfilling of the epoxy resin composition are less likely to occur. is there. Furthermore, the inorganic filler is less likely to bite into the connection part between the electronic component and the wiring board, and connection failure tends to be less likely to occur.

  The minimum particle diameter of the inorganic filler used in the present invention is not particularly limited as long as the effect of the present invention is achieved, but is preferably 0.075 μm or more, and preferably 0.080 μm or more. More preferably, it is 0.090 μm or more. If the minimum particle diameter of the inorganic particles is 0.075 μm or more, the viscosity tends to be difficult to increase greatly.

In the present invention, the “average particle diameter” of the inorganic filler means that the cumulative distribution is 50% in the cumulative distribution represented by the cumulative frequency, where the particle diameter is class and the volume is frequency using the following method. Means particle size.
Examples of the method for measuring the average particle size, the maximum particle size, and the minimum particle size of the inorganic filler include, for example, a method of measuring a large number of particles simultaneously using an apparatus such as dynamic light scattering and small angle X-ray scattering, an electron microscope Examples of the method include imaging with an atomic force microscope and measuring the particle size of each particle. Using a method such as liquid phase centrifugation, field flow fractionation, particle size exclusion chromatography, fluid dynamics chromatography or the like, a pretreatment for separating particles of 100 μm or more may be performed before measuring the particles. Moreover, when a measurement sample is the hardened | cured material of an underfill material, the ash obtained as a residue after processing at high temperature of 800 degreeC or more with a muffle furnace etc. can be measured by said method.

  In the present invention, in order to adjust the inorganic filler to have a peak between 0.1 and 10 μm in the particle size distribution, for example, as described above, the volume average particle diameter is 0.1 to 10 μm. For example, an inorganic filler is included.

The content of the inorganic filler in the present invention is not particularly limited as long as the effect of the present invention is achieved, and is preferably 20 to 70% by mass with respect to the total amount of the epoxy resin composition, and is preferably 30 to 30%. More preferably, it is 65 mass%, and it is further more preferable that it is 40-60 mass%.
If the content rate of an inorganic filler is 20 mass% or more, there exists a tendency for the intensity | strength of the hardened | cured material of an epoxy resin composition to improve, and reliability, such as temperature cycling resistance, to improve more. Moreover, if the content rate of an inorganic filler is 70 mass% or less, there exists a tendency for a viscosity to be low and for a filling property to be excellent.
As a method for measuring the content of the inorganic filler in the present invention, for example, it is calculated from the amount of ash obtained as a residue after treating the epoxy resin composition before or after curing at a high temperature of 800 ° C. or higher in a muffle furnace or the like. The method can be used.

  The epoxy resin composition of the present invention may contain other components in addition to the above-described components as long as the effects of the present invention are not impaired. Other components include, for example, release agents, surface treatment agents, flame retardants, leveling agents, antifoaming agents, thixotropic agents, thermal stabilizers, colorants, diluents, dyes, coupling agents, ion trapping agents, Surfactant, metal alkoxide, etc. are mentioned. The epoxy resin composition of the present invention is not limited to these, and various additives known in the art may be used as necessary.

  The epoxy resin composition of the present invention may contain a coupling agent. The coupling agent that can be used in the present invention is not particularly limited as long as the effects of the present invention are achieved. A primary amino group such as γ-anilinopropyltrimethoxysilane, a secondary amino group, and the like. Aminosilanes having at least one amino group selected from the group consisting of a group and a tertiary amino group, epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, methyltri Various silane compounds such as alkylsilanes such as methoxysilane, isocyanate silanes such as γ-isocyanatopropyltrimethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, vinylsilanes such as vinyltrimethoxysilane; isopropyl triisostearoyl titanate, etc. of Such as Tan-based compounds.

  The epoxy resin composition of this invention can use an ion trap agent as needed from a viewpoint of improving moisture resistance and a high temperature leaving property. The ion trap agent that can be used in the present invention is not particularly limited as long as it is an ion trap agent generally used in an epoxy resin composition for electronic parts. For example, the compound etc. which are represented by the following general formula (5) or general formula (6) are mentioned.

Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (5)
(In general formula (5), x is 0 <x ≦ 0.5, and m is a positive number.)
BiO _x (OH) _y (NO ₃ ) _z (6)
(In general formula (6), x is 0.9 ≦ x ≦ 1.1, y is 0.6 ≦ y ≦ 0.8, and z is 0.2 ≦ z ≦ 0.4.)

  As said ion trap agent, the compound of General formula (5) is available as a commercial item (Kyowa Chemical Industry Co., Ltd. make, brand name: DHT-4A), for example. Moreover, the compound of General formula (6) is commercially available (Toagosei Co., Ltd., brand name: IXE500).

  Examples of ion trapping agents other than those described above include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, etc., and these can be used alone or in combination of two or more. Also good.

In the epoxy resin composition of the present invention, a surfactant can be used as necessary from the viewpoint of improving fillet properties. The surfactant that can be used in the present invention is not particularly limited as long as it is a nonionic surfactant that is generally used in an epoxy resin composition for electronic parts. Nonionic surfactants include polyoxyalkylene alkyl ether surfactants such as polyoxyethylene alkyl ethers, sorbitan fatty acid ester surfactants, polyoxyethylene sorbitan fatty acid ester surfactants, and polyoxyethylene sorbitol fatty acid ester interfaces. Activator, glycerin fatty acid ester surfactant, polyoxyethylene fatty acid ester surfactant, polyoxyethylene alkylamine surfactant, alkyl alkanolamide surfactant, polyether modified silicone surfactant, aralkyl modified silicone surfactant, Various surfactants such as polyester-modified silicone surfactants and polyacrylic surfactants can be mentioned. Of these, polyether-modified silicone surfactants and aralkyl-modified silicone surfactants are effective in reducing the surface tension of the epoxy resin composition.
As these surfactants, commercially available products such as BYK-307, BYK-333, BYK-377, BYK-323 (trade names manufactured by Big Chemie Japan) and the like are available.

Furthermore, a silicone-modified epoxy resin can be added as a surfactant. The silicone-modified epoxy resin can be obtained as a reaction product of an organosiloxane having a functional group that reacts with an epoxy group and an epoxy resin. The silicone-modified epoxy resin is preferably liquid at room temperature. Examples of organosiloxanes having functional groups that react with epoxy groups are dimethylsiloxane, diphenylsiloxane, methylphenyl having at least one amino group, carboxyl group, hydroxyl group, phenolic hydroxyl group, mercapto group, etc. in one molecule. Examples thereof include siloxane.
These organosiloxanes are commercially available from Toray Dow Corning Co., Ltd. trade names BY16-799, BY16-871, BY16-004; Shin-Etsu Chemical Co., Ltd. trade names X-22-1821, KF-8010, etc. Is possible.

  The epoxy resin used to obtain the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin component of the epoxy resin composition, and is generally used for the epoxy resin composition for electronic parts. The epoxy resin currently used can be used. Specifically, glycidyl ether type epoxy resins obtained by reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin; including ortho cresol novolac type epoxy resins, A novolak-type epoxy resin obtained by epoxidizing a novolak resin obtained by condensation or co-condensation of a phenol compound and an aldehyde compound; a glycidyl ester-type epoxy resin obtained by reaction of a polybasic acid such as phthalic acid or dimer acid with epichlorohydrin; Glycidylamine type epoxy resin obtained by reaction of polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; obtained by oxidizing olefinic bonds with peracids such as peracetic acid Such as linear aliphatic epoxy resins and alicyclic epoxy resins. One of these may be used alone, or two or more may be used in combination. The epoxy resin used for obtaining the silicone-modified epoxy resin is preferably liquid at room temperature.

<Method for producing epoxy resin composition>
The epoxy resin composition of the present invention can be prepared by any method as long as the above various components can be uniformly dispersed and mixed. As a general method, the epoxy resin composition of the present invention is obtained by weighing predetermined components, mixing and kneading using a raking machine, mixing roll, planetary mixer, etc., and defoaming as necessary. Can do.

<Electronic component device and manufacturing method thereof>
The electronic component device of the present invention is sealed using the epoxy resin composition of the present invention.
As an electronic component device obtained using the epoxy resin composition of the present invention, a lead frame, a wired tape carrier, a rigid and flexible wiring board, glass, a support member (wiring substrate) such as a silicon wafer, a semiconductor chip, Electronic components such as active elements such as transistors, diodes, thyristors, and passive elements such as capacitors, resistors, resistor arrays, coils, and switches are mounted, and necessary parts are sealed with the epoxy resin composition of the present invention. Electronic component devices that can be used.
In particular, semiconductor devices in which a semiconductor element is flip-chip bonded to a wiring formed on a rigid or flexible wiring board or glass by bump connection are targeted. Specific examples include semiconductor devices such as flip chip BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film), and the epoxy resin composition of the present invention is a flip with excellent reliability. It is suitable as an underfill material for chips.

  The field of the flip chip in which the epoxy resin composition of the present invention is particularly suitable is a flip chip semiconductor element using a lead-free solder such as Sn-Ag-Cu as a bump material for connecting the wiring board and the semiconductor element. Good reliability can be maintained even for flip chips that are bump-bonded with lead-free solder, which is physically brittle compared to lead solder.

The method for sealing the electronic component using the epoxy resin composition of the present invention is not particularly limited as long as the electronic component device can be obtained. A method of infiltrating an epoxy resin composition into the gap between the electronic component and the wiring board using a capillary phenomenon after connecting the electronic component and the wiring board, the surface of the electronic component facing the wiring board, and the electronic component of the wiring board When the epoxy resin composition is applied to at least one of the opposite surfaces and the electronic component is connected by thermocompression bonding, the connection between the electronic component and the wiring board via the metal bump and the curing of the epoxy resin composition , A method in which an epoxy resin composition is applied onto a wiring board, an electronic component is mounted, and then heated in a reflow furnace to perform connection and curing in a batch, an epoxy resin composition on the electronic component A method in which this electronic component is thermocompression bonded to a wiring board to perform connection and curing at once, and an epoxy resin composition is applied onto a silicon wafer before being separated into pieces by dicing. The semiconductor device obtained was diced to be after surge of a method performed collectively and curing connection thermocompression bonding or the like to the wiring board.
In the present invention, the B stage is defined by JIS K6900: 1994.
In particular, when an epoxy resin composition is applied to at least one of the surface of the electronic component facing the wiring substrate and the surface of the wiring substrate facing the electronic component, and the electronic component is connected by thermocompression bonding, A pre-coating method in which the connection between the component and the wiring board via the metal bumps and the curing of the epoxy resin composition are collectively performed is preferable.

Hereinafter, the manufacturing method of the electronic component device by the pre-coating method will be described in detail.
The method of manufacturing an electronic component device according to the pre-coating method of the present invention is to manufacture an electronic component device by joining an electronic component and a wiring board via metal bumps, and the electronic component device includes: An adhesion step of attaching the epoxy resin composition of the present invention to at least one of the opposing surface and the surface of the wiring substrate facing the electronic component; and the metal bumps between the electronic component and the wiring substrate. The gap between the electronic component and the wiring board is filled with the epoxy resin composition, and the electronic component and the wiring board are brought into contact with each other via the metal bumps. Pressure treatment and at least one of the electronic component and the wiring board during and after the pressurization step and before the heat treatment in a state where the electronic component and the wiring board are pressed and contacted via the metal bumps. The electronic component and the wiring substrate are joined via the metal bump, and may have a heat treatment step of curing the epoxy resin composition.
According to the method for manufacturing an electronic component device according to the pre-coating method of the present invention, it is possible to collectively perform bonding of the electronic component and the wiring board through the metal bumps and curing of the epoxy resin composition in the heat treatment step. Therefore, the process can be simplified.

Hereinafter, a method of manufacturing an electronic component device by a pre-coating method will be described with reference to the drawings. In addition, in the manufacturing method of the following electronic component apparatus, the aspect which adheres the epoxy resin composition of this invention to the surface of the side facing the electronic component of a wiring board is demonstrated. Further, the metal bump is provided on the electronic component side, and the electronic component and the wiring board are joined via the metal bump. However, the present invention is not limited to these embodiments.
FIG. 1 is a process explanatory diagram of a method of manufacturing an electronic component device by a pre-coating method.
In FIG. 1, 1 is a semiconductor chip (electronic component), 2 is a solder bump, 3 is a connection pad, 4 is a solder resist, 5 is a wiring board, and 6 is a sealing resin (the epoxy resin composition of the present invention).

  First, in FIG. 1A, a sealing resin 6 which is an epoxy resin composition of the present invention is provided on the surface of the wiring board 5 where the connection pads 3 are provided (the side of the wiring board 5 facing the semiconductor chip 1). Is applied (attachment process). Examples of the method for applying the sealing resin 6 include a dispensing method, a casting method, and a printing method. The application region of the sealing resin 6 may be applied to the entire region of the wiring substrate 5 where the connection pads 3 are provided, or may be applied to a part of the region of the wiring substrate 5 where the connection pads 3 are provided. May be. The sealing resin 6 flows when the wiring substrate 5 and the semiconductor chip 1 are brought into contact with each other via the solder bumps 2 by applying the sealing resin 6 to a part of the region where the connection pads 3 of the wiring substrate 5 are provided. Therefore, it is preferable because it is filled between the wiring substrate 5 and the semiconductor chip 1. The coating pattern of the sealing resin 6 on the wiring substrate 5 is preferably a cruciform along the diagonal line of the region of the wiring substrate 5 where the semiconductor chip 1 is disposed.

Next, in FIG. 1B, the semiconductor chip 1 and the wiring board 5 are opposed to each other while being pressed through the solder bumps 2, thereby filling the gap between the semiconductor chip 1 and the wiring board 5 with the sealing resin 6. In addition, the semiconductor chip 1 and the connection pads 3 of the wiring substrate 5 are brought into contact with each other through the solder bumps 2 (pressure process).
The pressurizing condition for filling the sealing resin 6 in the gap between the semiconductor chip 1 and the wiring substrate 5 is preferably 0.001 to 100N, more preferably 0.005 to 50N, and further preferably 0.01 to 10N. preferable.
Moreover, as a pressurization condition at the time of making the semiconductor chip 1 and the connection pad 3 of the wiring board 5 contact via the solder bump 2, 0.002-200N is preferable, 0.01-100N is more preferable, and 0.1. 02 to 20N are more preferable. Under this pressure condition, the semiconductor chip 1 and the connection pads 3 of the wiring board 5 may be joined via the solder bumps 2 in a heat treatment step described later.

During at least one of the pressurizing step and after the pressurizing step, the semiconductor chip 1 and the wiring pads 5 of the wiring substrate 5 are heat-treated in a state where they are pressed and contacted via the solder bumps 2 and the semiconductor chip 1 and the wiring. The connection pads 3 of the substrate 5 are joined via the solder bumps 2 and the sealing resin 6 is cured (heat treatment step).
As heating conditions, 150-300 degreeC is preferable, 200-280 degreeC is more preferable, 220-260 degreeC is further more preferable. At this time, the sealing resin 6 is cured.
Furthermore, you may heat for 0.5 to 6 hours in the range of 120-200 degreeC in order to make hardening of the sealing resin 6 sufficient as needed.
Through the above steps, the electronic component device of the present invention is manufactured.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.

The synthesis method of OH-DHC used in the Examples and the ¹ H-NMR chart of the compound are shown in FIG.

<Synthesis of OH-DHC>
In a three-neck separable flask equipped with a reflux tube, 40.0 g of resorcinol (manufactured by Wako Pure Chemical Industries, Ltd.), 27.5 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), Amberyst 15 (H) (manufactured by MP Biochemicals) 6.00 g and 600 g of toluene were added, and the mixture was heated to reflux for 6 hours. The solution after the reaction was filtered to remove Amberlyst 15 (H), and then the filtrate was allowed to stand for 12 hours to precipitate crystals. The precipitated crystal was filtered, washed with 200 g of toluene, and then dried under reduced pressure to obtain 38.7 g (yield 65%) of OH-DHC represented by the formula (7).

(Examples 1-8, Comparative Examples 1-16)
(A) Epoxy resin / epoxy resin 1: bisphenol F type epoxy resin having an epoxy equivalent of 160 g / eq (manufactured by Nippon Steel Chemical Co., Ltd., trade name “YDF-8170C”)
Epoxy resin 2: Epoxy resin obtained by epoxidizing aminophenol having an epoxy equivalent of 95 g / eq (trade name “jER630” manufactured by Mitsubishi Chemical Corporation)

(B) Curing agent / curing agent 1: 6-membered ring lactone having an active hydrogen equivalent of 148 g / eq (DHC, manufactured by Wako Pure Chemical Industries, Ltd., trade name “3,4-dihydrocoumarin”)
Curing agent 2: 6-membered ring lactone having an active hydrogen equivalent of 82 g / eq (OH-DHC, synthetic product represented by the above formula (7))
Curing agent 3: cyclic acid anhydride having an active hydrogen equivalent of 234 g / eq (trade name “YH306” manufactured by Mitsubishi Chemical Corporation)
Curing agent 4: Liquid phenolic resin having an active hydrogen equivalent of 111 g / eq (Maywa Kasei Co., Ltd., trade name “MEH-8400”)

(C) Curing accelerator / curing accelerator: reaction product of 5-hydroxyisophthalic acid and 2-ethyl-4-methylimidazole (manufactured by Nippon Soda Co., Ltd., developed product name “HIPA-2E4MZ”)

Modified epoxy resin / rubber particles (acrylonitrile-butadiene-methacrylic acid-divinylbenzene copolymer (trade name “XER-91P” manufactured by JSR Corporation) and bisphenol F type epoxy resin (YDF-8170C, epoxy equivalent 160 g / eq) And a modified epoxy resin in which rubber particles are dispersed by heating and melting at 100 ° C. for 60 minutes in a mass ratio of 1: 4)

Thixotropic agent (first inorganic particles)
The average particle size of the first inorganic particles was measured as follows.
Using a transmission electron microscope (product name “JEM-2100F”, JEOL Ltd.), 50 particles having a particle size of 70 nm or less were randomly selected and their particle sizes were measured. The average particle diameter was averaged. More specifically, it was performed as follows. The first inorganic particles were added to a solvent (methyl ethyl ketone) at 0.1% by mass, and the mixture was vibrated with an ultrasonic homogenizer for 30 minutes and dispersed to prepare a dispersion. A collodion membrane affixed mesh (200 mesh Cu, manufactured by Nissin EM Co., Ltd.) was immersed in the dispersion and dried under conditions of 25 ° C. for 20 minutes to prepare an observation sample. The observation sample was measured using a transmission electron microscope (product name “JEM-2100F”, manufactured by JEOL Ltd.) under the condition of an acceleration voltage of 200 kV. In addition, when the particle | grains in an image were not perfect circles, the major axis was measured as the particle diameter.
Thixotropic agent: silica particles having an average particle diameter of 12 nm and surface-treated with alkylsilane (trade name “R-805” manufactured by Nippon Aerosil Co., Ltd.)

Inorganic filler (second inorganic particles)
The average particle size of the second inorganic particles was measured as follows.
(1) Preparation of sample The second inorganic particles were added to a solvent (water) at 5 wt%, and the mixture was vibrated with an ultrasonic homogenizer for 30 minutes and dispersed to prepare a sample.
(2) Measurement Measured with a laser diffraction particle size distribution analyzer LA-920 (trade name, manufactured by Horiba, Ltd.). The measurement conditions were such that the dispersion medium had a refractive index of 1.00 (in the case of water) and the second inorganic particles had a refractive index of 1.47 (in the case of silica particles).
(3) Calculation of average particle size The particle size at an integrated value of 50% (volume basis) in the particle size distribution was defined as the average particle size.
Inorganic filler 1: volume average particle diameter 0.5 μm, maximum particle diameter 5 μm, spherical silica particles whose surface is treated with a coupling agent (trade name “SE-2050-SEJ” manufactured by Admatechs Co., Ltd.)
Inorganic filler 2: Spherical silica particles having an average particle size of 10.7 μm and a maximum particle size of 42.0 μm (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “FB-105XFC”)

(Other various additives)
Coupling agent: γ-glycidoxypropyltrimethoxysilane Ion trap agent (ion trapper): Bismuth ion trap agent (trade name “IXE-500” manufactured by Toagosei Co., Ltd.)

  The above components are blended in the parts by mass shown in Tables 1 and 2, respectively, kneaded and dispersed with a three roll and a raking machine, and then vacuum degassed to produce the epoxy resin compositions of Examples and Comparative Examples. did. In addition, the compounding unit in a table | surface is a mass part.

  The epoxy resin composition obtained by Examples 1-8 and Comparative Examples 1-16 was evaluated by each test shown below. The evaluation results are shown in Tables 3 and 4.

<Gelification time>
0.05 ml of the epoxy resin composition was dropped on a hot plate at 260 ° C. and stirred with a spatula so as not to spread too much. After dropping, the viscosity of the epoxy resin composition increased, and the time until the epoxy resin composition was cut without stringing when the spatula was lifted up was defined as the gel time.

<Connectivity>
Wiring substrate (size: 14 mm × 14 mm × 0.30 mm, core layer: E-679FG (trade name, manufactured by Hitachi Chemical Co., Ltd.), solder resist: AUS-308 (trade name, manufactured by Taiyo Holdings Co., Ltd.), substrate plating: About 3 mg of the epoxy resin composition was applied to a chip mounting portion of Ni (5.0 μm) + Pd (0.30 μm) + Au (0.35 μm)) using a dispenser. A wiring board coated with an epoxy resin composition is placed on a stage heated to 80 ° C., and a chip (size: 7.3 mm × 7.3 mm × 0.15 mm, bump: copper (height 30 μm) + solder (material: SnAg) , Height: 15 μm), bump pitch: 80 μm, number of bumps: 328), thermocompression bonding was performed under conditions of weight: 7.5 N, temperature / time: 260 ° C./5 seconds, and then 165 ° C., 2 A semiconductor device was obtained by curing under time conditions.
For each epoxy resin composition, a semiconductor device was produced by the above method, and the presence or absence of disconnection of the wiring and the connection part was confirmed by a continuity test, and (number of defective packages) / (number of evaluation packages) was defined as connectivity. .

<Void properties>
The semiconductor device manufactured by the above method is observed using an ultrasonic flaw detector AT-5500 (Hitachi Construction Machinery Co., Ltd.), and the presence or absence of voids is determined as A (void area is 1% or less of the total area), B ( The void area was classified into three stages, ie, void area exceeding 1% and 5% or less) and C (void area exceeding 5% of the total area).

Examples 1 to 8 are epoxy resin compositions containing a 6-membered ring lactone as a curing agent, and it can be seen that these have good connectivity and voidability even when the gelation time is long. On the other hand, in Comparative Examples 1-8, it turns out that it is inferior to the connectivity and void property which are difficult to lengthen gelation time.
From the above results, when the epoxy resin composition of the present invention is used as an underfill material of a pre-coating method, sufficient connectivity can be obtained by thermocompression bonding even when the gelation time is long, and voids can be obtained. It can be seen that a sufficiently reduced resin cured product can be obtained.

Claims (6)

  An epoxy resin composition comprising (A) an epoxy resin, (B) a 6-membered ring lactone having an aromatic skeleton, (C) a curing accelerator, and (D) an inorganic filler having an average particle diameter of 0.1 to 10 μm. .   (A) an epoxy resin, (B) a 6-membered ring lactone having an aromatic skeleton, (C) a curing accelerator, (D) an inorganic filler, and (D) the inorganic filler has a particle size distribution of 0.1. An epoxy resin composition having an inorganic filler having a peak between 10 μm and 10 μm.   The epoxy resin composition according to claim 1 or 2, wherein the aromatic skeleton of (B) is a benzene ring or a naphthalene ring. The 6-membered ring lactone of (B) is condensed to a benzene ring or a naphthalene ring as an aromatic skeleton, and is represented by the following general formula (1) or (2). The epoxy resin composition described in 1.

(In the formula, R _{1 to} R ₁₄ may be the same or different. R _{1 to} R ₁₄ have a hydrogen atom, a hydroxyl group, or a carbon atom number of 1 to 20, and are linear or branched. Or an aromatic or heteroaromatic skeleton or a 6-membered lactone skeleton, or is bonded to the skeleton by a bridging atom or bridging group, preferably having 6 to 20 carbon atoms. An aryl, alkaryl or aralkyl group, and / or adjacent groups R ₅ and R ₆ , or R ₆ and R ₇ , R ₇ and R ₈ , R ₉ and R ₁₀ , R ₁₁ and R ₁₂ , R ₁₂ and R ₁₃ or _{R 13} and _{R 14,} may form a 6-membered ring lactone skeleton, and / _or, any of R 5 to R _8, and _R 9 _{to R 14,} the general formula ( ) Or (aliphatic to a second lactone represented by II), a "bridging group" alicyclic or aromatic.)   The electronic component apparatus sealed using the epoxy resin composition of any one of Claims 1-4.   An electronic component device manufacturing method for manufacturing an electronic component device by joining an electronic component and a wiring substrate through metal bumps, the surface of the electronic component facing the wiring substrate and the wiring substrate An adhesion step of attaching the epoxy resin composition according to any one of claims 1 to 4 to at least one of surfaces facing the electronic component, the electronic component and the wiring board being attached to the metal By facing the pressure through the bump, the epoxy resin composition is filled in the gap between the electronic component and the wiring board, and the electronic component and the wiring board are contacted via the metal bump. And a heat treatment in a state in which the electronic component and the wiring board are in pressure contact with each other through the metal bumps before and during at least one of the pressure step and the pressure step. The electronic component and the wiring substrate are joined via the metal bump, and a method of manufacturing an electronic component device and a heat treatment step of curing the epoxy resin composition.

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