JP2018062606A - Underfill material, electronic component device and method for producing electronic component device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an underfill material that prevents cracking of a solder resist in reflowing, and has excellent temperature cycle resistance.SOLUTION: An underfill material contains (A) an epoxy resin, (B) a curing agent and (C) an inorganic filler. When made into a cured product, the underfill material shows a thermal expansion coefficient of 30 ppm/°C or less, at a glass transition temperature or lower, measured by TMA (thermomechanical analysis), and shows a storage elastic modulus of 0.10 GPa or less, at 240°C, measured by DMA (dynamic mechanical analysis).SELECTED DRAWING: None

Description

  The present invention relates to an underfill material, an electronic component device, and a method for manufacturing an 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 adhesiveness with inserts.

In electronic component devices mounted with bare chips such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package), an underfill material is widely used as a sealing material.
In addition, in an electronic component device (flip chip) in which an electronic component such as a semiconductor element is directly bump-connected to a wiring board using a ceramic, glass epoxy resin, glass imide resin, polyimide film or the like as a substrate, the bump-connected electronic component An epoxy resin composition is used as an underfill material for filling a gap (gap) between the wiring board and the wiring board. The underfill material plays an important role in protecting electronic components from temperature and humidity and mechanical external force.

  Here, an epoxy resin composition for sealing excellent in moisture-resistant adhesive strength and low-stress property, and an electronic component device having high reliability (moisture resistance and thermal shock resistance) provided with an element sealed thereby. Therefore, (A) a liquid epoxy resin, (B) a curing agent containing a liquid aromatic amine, (C) a rubber particle and (D) an epoxy resin composition for sealing containing an inorganic filler, and this sealing An electronic component device including an element sealed with an epoxy resin composition for use is disclosed (for example, see Patent Document 1).

JP 2001-270976 A

However, the progress of semiconductor technology is remarkable, and semiconductors and wiring boards are becoming larger and wiring boards are being made thinner. Therefore, in the flip-chip method for bump connection, if the elastic modulus at the reflow temperature of the cured underfill material is high, the cured underfill material cannot follow the expansion of the bump, and the solder resist formed on the wiring board Stress tends to concentrate on When stress concentrates on the solder resist, cracks may occur in the solder resist on the wiring board due to expansion of the bumps during reflow.
The elastic modulus of the cured product of the underfill material can be lowered by reducing the amount of the inorganic filler contained in the underfill material, but if the inorganic filler is reduced too much, the thermal expansion coefficient increases, and in the temperature cycle test May cause problems due to expansion and contraction of the cured product of the underfill material.

As described above, underfill materials are required to solve various problems as semiconductor technology advances.
The present invention has been made in view of such circumstances, an underfill material in which the occurrence of cracks in the solder resist during reflow is suppressed and excellent in temperature cycle resistance, and the reliability sealed thereby. An object of the present invention is to provide a high electronic component device and a manufacturing method thereof.

  As a result of intensive studies to solve the above problems, the inventors of the present invention assumed that the composition of the underfill material includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and is cured. The thermal expansion coefficient below the glass transition temperature measured by TMA (thermomechanical analysis) is 30 ppm / ° C. or less, and the storage elastic modulus at 240 ° C. measured by DMA (dynamic viscoelasticity measurement) is 0.00. The inventors have found that the above object can be achieved by setting the pressure to 10 GPa or less, and have completed the present invention.

The present invention relates to the following.
<1> (A) includes an epoxy resin, (B) a curing agent, and (C) an inorganic filler,
The thermal expansion coefficient below the glass transition temperature measured by TMA (thermomechanical analysis) when cured is 30 ppm / ° C. or less, and the storage modulus at 240 ° C. measured by DMA (dynamic viscoelasticity measurement). An underfill material of 0.10 GPa or less.
The underfill material as described in <1> whose glass transition temperature measured by TMA (thermomechanical analysis) when it is set as <2> hardened | cured material is 60 to 150 degreeC.
The underfill material as described in <1> or <2> whose storage elastic modulus in 25 degreeC measured by DMA (dynamic viscoelasticity measurement) when it is set as <3> hardened | cured material is 5GPa-10GPa.
<4> The underfill material according to any one of <1> to <3>, further comprising (D) a flexibilizer.
<5> The underfill material according to any one of <1> to <4>, further comprising (E) a surfactant.
<6> The underfill material according to any one of <1> to <5>, further comprising (F) an ion trap agent.
<7> The underfill material according to any one of <1> to <6>, further comprising (G) a curing accelerator.
<8> The underfill material according to any one of <1> to <7>, further comprising (H) a coupling agent.
<9> The underfill material according to any one of <1> to <8>, further comprising (I) an antioxidant.
<10> The underfill material according to any one of <1> to <9>, further comprising (J) an organic solvent, wherein the content of the organic solvent is 10% by mass or less.
<11> The underfill material according to any one of <1> to <10>, wherein the (B) curing agent is an aromatic amine compound.
<12> a wiring board;
An electronic component disposed on the wiring board and electrically connected to the wiring board via a connection portion;
At least a cured product of the underfill material according to any one of <1> to <11> that seals a connection portion between the wiring board and the electronic component;
An electronic component device comprising:
<13> The electronic component device according to <12>, wherein the connection portion does not contain lead.
<14> The electronic component device according to <12> or <13>, wherein the connection portion includes copper.
<15> A method of manufacturing an electronic component device in which an electronic component and a wiring board are electrically connected via a connecting portion,
The under surface according to any one of <1> to <11>, wherein at least one of a surface of the electronic component facing the wiring substrate and a surface of the wiring substrate facing the electronic component is disposed. A supply process for supplying a fill material;
A connection step of connecting the electronic component and the wiring board via the connection portion and curing the underfill material.
<16> A method for manufacturing an electronic component device in which an electronic component and a wiring board are electrically connected via a connecting portion,
A filling step of filling the underfill material according to any one of <1> to <11> in a gap between the connected electronic component and the wiring board;
And a curing step of curing the underfill material.

  According to the present invention, an underfill material that suppresses the occurrence of cracks in a solder resist during reflow and has excellent temperature cycle resistance, and a highly reliable electronic component device sealed thereby and a method for manufacturing the same are provided. Provided.

In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .
Moreover, the numerical value range shown using "to" in this specification shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively.
In the numerical ranges described stepwise 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 numerical range. Good. Further, 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 values shown in the examples.
In the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. It means the content rate of.
In the present specification, the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
In this specification, the term “layer” or “film” refers to a part of the region in addition to the case where the layer or the film is formed when the region where the layer or film exists is observed. It is also included when it is formed only.

<Underfill material>
The underfill material of the present disclosure includes (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, and has a glass transition temperature or less measured by TMA (thermomechanical analysis) when a cured product is obtained. The thermal expansion coefficient is 30 ppm / ° C. or less, and the storage elastic modulus at 240 ° C. measured by DMA (dynamic viscoelasticity measurement) is 0.10 GPa or less.

  Hereinafter, each component constituting the underfill material of the present disclosure will be described.

((A) Epoxy resin)
The epoxy resin of component (A) used in the present disclosure is not particularly limited as long as it has one or more epoxy groups in one molecule, and an epoxy resin generally used for underfill materials may be used. it can.
The kind of epoxy resin used by this indication is not specifically limited. Epoxy resins include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A, naphthalene diol, alkyl diol, etc., and glycidyl ether type epoxy resins obtained by reaction with epichlorohydrin, orthocresol novolac type epoxy. Novolak type epoxy resin obtained by epoxidizing novolak resin obtained by condensation or cocondensation of phenols and aldehydes represented by resin, obtained by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin obtained by reaction of amine compound such as aminophenol, diaminodiphenylmethane, isocyanuric acid and epichlorohydrin, olefin bond Obtained by oxidizing a peracid such as peracetic acid linear aliphatic epoxy resins, and the like alicyclic epoxy resins may be used in combination of two or more even with these alone.
Among these, from the viewpoint of fluidity, a liquid bisphenol-type epoxy resin that is one of glycidyl ether-type epoxy resins is preferable, and from the viewpoint of heat resistance, adhesiveness, and fluidity, a liquid glycidylamine-type epoxy resin is preferable.

The above two types of epoxy resins may be used alone or in combination of two types, but the blending ratio is 20 mass in total with respect to the total amount of the epoxy resin in order to exhibit its performance. % Or more, preferably 30% by mass or more, and more preferably 50% by mass or more.
In addition, the underfill material of the present disclosure may be used in combination with a solid epoxy resin as long as the effects of the present disclosure are achieved. From the viewpoint of the fluidity of the underfill material, the solid epoxy resin used in combination is preferably 20% by mass or less based on the total amount of the epoxy resin.

To make the coefficient of thermal expansion below the glass transition temperature measured by TMA (thermomechanical analysis) when the underfill material is a cured product to 30 ppm / ° C. or less, the aromatic ring in the molecule occupies the total amount of the epoxy resin. The proportion of the epoxy resin contained is preferably 65% by mass or more, and more preferably 70% by mass or more.
In order to set the storage elastic modulus at 240 ° C. measured by DMA (dynamic viscoelasticity measurement) when the underfill material is a cured product to 0.10 GPa or less, a trifunctional or higher functional epoxy resin occupying the total amount of the epoxy resin Is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

In addition, a liquid epoxy resin means that it is a liquid epoxy resin at normal temperature (25 degreeC). Specifically, it means that the viscosity measured with an E-type viscometer is 1000 Pa · s or less at 25 ° C. Specifically, the viscosity is measured using an E-type viscometer EHD type (cone angle: 3 °, cone diameter: 28 mm), measuring temperature: 25 ° C., sample volume: 0.7 ml, and the number of rotations with reference to the following. The value after 1 minute from the start of measurement is taken as the measurement value after setting according to the assumed viscosity.
(1) When the assumed viscosity is 100 Pa · s to 1000 Pa · s: the rotation speed is 0.5 rotation / min. (2) When the assumed viscosity is less than 100 Pa · s: the rotation speed is 5 rotation / min. An epoxy resin means a solid epoxy resin at room temperature (25 ° C.).

  The purity of the epoxy resin, especially the amount of hydrolyzable chlorine, is preferable because it is related to the corrosion of the aluminum wiring on the IC and other elements. In order to obtain an underfill material with excellent moisture resistance, the hydrolyzability of the epoxy resin The amount of chlorine is preferably 500 ppm or less. Here, the amount of hydrolyzable chlorine is a value obtained by dissolving 1 g of an epoxy resin of a sample in 30 ml of dioxane, adding 5 ml of a 1N-KOH methanol solution and refluxing for 30 minutes, and then obtaining by potentiometric titration. is there.

From the viewpoint of viscosity adjustment, the epoxy equivalent of the epoxy resin is preferably 90 g / eq to 450 g / eq, more preferably 90 g / eq to 350 g / eq, and 90 g / eq to 250 g / eq. Is more preferable.
The epoxy equivalent of the epoxy resin is measured by dissolving the weighed epoxy resin in a solvent such as methyl ethyl ketone, adding acetic acid and a tetraethylammonium bromide acetic acid solution, and then performing potentiometric titration with a perchloric acid acetic acid standard solution. An indicator may be used for this titration.

The content rate of an epoxy resin is not specifically limited, For example, it is preferable that it is 10 mass%-50 mass% as a ratio to the solid content of an underfill material, and it is 15 mass%-45 mass% Is more preferable, and it is further more preferable that it is 20 mass%-40 mass%.
In the present disclosure, the “solid content” of the underfill material means a remaining component obtained by removing a volatile component such as an organic solvent from the underfill material.

((B) curing agent)
There is no restriction | limiting in particular in the hardening agent of (B) component used by this indication.
Examples of amines having aromatic rings (aromatic amine compounds) as curing agents include diethyltoluenediamine, 1,3,5-triethyl-2,6-diaminobenzene, 3,3′-diethyl-4,4 ′. -Diaminodiphenylmethane, 3,5,3 ', 5'-tetramethyl-4,4'-diaminodiphenylmethane and the like.
These aromatic amine compounds are commercially available as Epicure-W, Epicure-Z (trade name, manufactured by Mitsubishi Chemical Corporation), Kayahard AA, Kayahard AB, Kayahard AS (manufactured by Nippon Kayaku Co., Ltd.). Product name), Totoamine HM-205 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Adeka Hardener EH-101 (trade name, manufactured by ADEKA Co., Ltd.), Epomic Q-640, Epomic Q-643 (Product manufactured by Mitsui Chemicals, Inc.) Name), DETDA80 (trade name manufactured by Lonza), etc. are available, and these may be used alone or in combination of two or more.

  When an aromatic amine compound is used as the curing agent, examples of the aromatic amine compound include 3,3′-diethyl-4,4′-diaminodiphenylmethane and diethyltoluenediamine from the viewpoint of storage stability of the underfill material. Is preferred. Examples of diethyltoluenediamine include 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine. When an aromatic amine compound is used as a curing agent, the curing agent contains 3,3′-diethyl-4,4′-diaminodiphenylmethane or 3,5-diethyltoluene-2,4-diamine in an amount of 50% by mass or more. Is preferred.

  Examples of acid anhydrides as curing agents include phthalic anhydride, maleic anhydride, methyl hymic acid anhydride, hymic acid anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride , Methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride maleic acid adduct, benzophenone tetracarboxylic anhydride, trimellitic anhydride, pyrone anhydride Various acid anhydrides such as melicic acid, hydrogenated methyl nadic acid anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride and the like obtained by Diels-Alder reaction from maleic anhydride and diene compound. These may be used alone or in combination of two or more.

  When an acid anhydride is used as the curing agent, for example, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferable as the acid anhydride from the viewpoint of reducing the viscosity of the underfill material. When an acid anhydride is used as the curing agent, the curing agent preferably contains 50% by mass or more of tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

In addition, the underfill material includes a curing agent generally used in an underfill material such as a phenolic curing agent in addition to the aromatic amine compound and the acid anhydride as long as the effect of the present disclosure is achieved. Can be used together.
As the curing agent, an aromatic amine compound having good moisture resistance reliability is preferable because the cured product is hardly hydrolyzed.

  The equivalent ratio of the number of equivalents of epoxy resin contained in the underfill material to the number of equivalents of curing agent (number of equivalents of curing agent / number of equivalents of epoxy resin) is preferably 0.7 to 1.3. More preferably, it is 0.8 to 1.2, and more preferably 0.9 to 1.1. When the ratio is 0.7 or more, there is no shortage of the curing agent, the number of epoxy resins that do not affect the reaction decreases, and the reliability tends not to decrease. On the other hand, if the ratio is 1.3 or less, the excess curing agent decreases, so the glass transition temperature does not become too high, and the elastic modulus at high temperature of the cured product does not become too high. There is a tendency that the warpage is less likely to occur.

((C) inorganic filler)
As the inorganic filler of the component (C) used in the present disclosure, silica such as spherical silica and crystalline silica, calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, Examples thereof include powders such as aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, and titania, or beads and glass fibers formed by spheroidizing them.
Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate. These inorganic fillers may be used alone or in combination of two or more. Among these, spherical silica is more preferable from the viewpoints of fluidity and permeability into the fine gaps of the underfill material.

In the case of spherical silica, the average particle diameter of the inorganic filler is preferably in the range of 0.05 μm to 20 μm, and more preferably in the range of 0.2 μm to 10 μm. If the average particle size is 0.05 μm or more, the dispersibility in the liquid resin is improved, the viscosity is hardly increased, and the flow characteristics of the underfill material tend to be improved. If the average particle size is 20 μm or less, there is a tendency that sedimentation is unlikely to occur, and the permeability and fluidity to the fine gaps as the underfill material are improved, making it difficult to cause unfilling of voids and underfill materials. is there.
Here, the average particle diameter is a particle diameter corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is obtained with the total volume of the particles being 100%, and particle size distribution measurement using a laser diffraction scattering method is performed. It can be measured with an apparatus or the like.

  The content of the inorganic filler is preferably in the range of 20% by mass to 90% by mass, more preferably in the range of 30% by mass to 85% by mass, and still more preferably as a proportion of the solid content of the underfill material. It is 40 mass%-80 mass%. If the content is 20% by mass or more, the coefficient of thermal expansion is unlikely to decrease, and the temperature cycle resistance of the cured product of the underfill material tends to be more excellent, and if it is 90% by mass or less, the viscosity of the underfill material. Are less likely to increase, and tend to be less likely to cause a decrease in fluidity, permeability and dispensing properties.

((D) Flexibilizer)
The underfill material of the present disclosure can be blended with various flexing agents from the viewpoint of improving thermal shock resistance and reducing stress on electronic components such as semiconductor elements.
Although there is no restriction | limiting in particular as a softening agent, A rubber particle is preferable. Examples of the rubber particles include rubber particles of silicone rubber and rubber particles of synthetic rubber other than silicone rubber (hereinafter sometimes simply referred to as “synthetic rubber”).
Examples of synthetic rubber rubber particles include rubber particles such as styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic rubber (AR). . Among these, acrylic rubber rubber particles are preferable from the viewpoint of heat resistance and moisture resistance, and core-shell acrylic polymers, that is, core-shell acrylic rubber particles are more preferable.

  Examples of silicone rubber rubber particles include silicone rubber particles obtained by crosslinking polyorganosiloxanes such as linear polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane, and the surface of the silicone rubber particles is coated with a silicone resin. A core-shell polymer particle having a core of solid silicone particles obtained by emulsion polymerization and a shell of a polymer such as an acrylic resin, and a spherical shape in which the surface of dimethyl type solid silicone rubber particles is modified with an epoxy group Examples thereof include silicone particles. These silicone rubber particles can be used in an amorphous or spherical shape. In order to keep the viscosity related to the moldability of the underfill material low, it is preferable to use a spherical material. These silicone rubber particles are commercially available from Toray Dow Corning Co., Ltd., Shin-Etsu Chemical Co., Ltd. and the like.

  The average particle diameter of these flexibilizers is desirably smaller in order to uniformly modify the underfill material, and the average particle diameter is preferably in the range of 0.05 μm to 10 μm, preferably 0.1 μm to 5 μm. More preferably, it is the range. If the average particle size is 0.05 μm or more, it tends to be excellent in dispersibility in the underfill material, and if it is 10 μm or less, the stress tends to decrease, and further penetrates into the fine gap as the underfill material. It tends to be less likely to cause unfilled voids and underfill materials.

  The content of the flexibilizer is preferably set in the range of 1% by mass to 30% by mass, more preferably 2% by mass to 20% by mass with respect to the entire epoxy resin. If the content of the flexibilizer is 1% by mass or more, the effect of reducing the stress tends to be improved. If the content is 30% by mass or less, the viscosity of the underfill material hardly increases, and the moldability (flow characteristics, etc.) ).

((E) Surfactant)
Various surfactants can be mix | blended with the underfill material of this indication from a viewpoint of reduction of generation | occurrence | production of the void at the time of shaping | molding, and the improvement of the adhesive force by the improvement of the wettability to various to-be-adhered bodies.
The surfactant is not particularly limited, but nonionic surfactants are preferable, polyoxyalkylene alkyl ether surfactants such as polyoxyethylene alkyl ether surfactants, and sorbitan fatty acid ester surfactants. , Polyoxyethylene sorbitan fatty acid ester surfactant, polyoxyethylene sorbitol fatty acid ester surfactant, glycerin fatty acid ester surfactant, polyoxyethylene fatty acid ester surfactant, polyoxyethylene alkylamine surfactant Surfactants such as alkyl alkanolamide surfactants, polyether modified silicone surfactants, aralkyl modified silicone surfactants, polyester modified silicone surfactants, polyacrylic surfactants, and the like. Be used et alone may be used in combination of two or more. These surfactants are commercially available from Big Chemie Japan, Kao Corporation and the like.

Further, 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 normal temperature (25 ° C.). Examples of organosiloxanes having a functional group that reacts with an epoxy group are dimethylsiloxane, diphenylsiloxane, methylphenyl having at least one amino group, carboxy group, hydroxyl group, phenolic hydroxyl group, mercapto group, etc. in one molecule. Examples thereof include siloxane. The weight average molecular weight of the organosiloxane is preferably in the range of 500 to 5,000. If the weight average molecular weight of the organosiloxane is 500 or more, the compatibility with the epoxy resin or the like is not improved excessively and the effect as an additive tends to be exhibited. If the weight average molecular weight of the organosiloxane is 5000 or less, it is difficult to be incompatible with an epoxy resin or the like. Therefore, when the underfill material is cured, the silicone-modified epoxy resin hardly separates or exudes from the underfill material, and is bonded. It tends not to cause problems that impair the performance or appearance.
The weight average molecular weight of the organosiloxane is determined by conversion using a standard polystyrene calibration curve from a molecular weight distribution measured using GPC (gel permeation chromatography).

  The epoxy resin for obtaining the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin system of the underfill material, and an epoxy resin generally used for the underfill material can be used. Representative examples of epoxy resins include glycidyl ether type epoxy resins and orthocresol novolak type epoxy resins obtained by the reaction of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A and the like with epichlorohydrin. Glycidyl ester obtained by reaction of a polybasic acid such as phthalic acid and dimer acid with epichlorohydrin obtained by epoxidizing a novolak resin obtained by condensation or cocondensation of phenols and aldehydes Type epoxy resin, diaminodiphenylmethane, glycidylamine type epoxy resin obtained by reaction of epichlorohydrin with amine compounds such as diaminodiphenylmethane and isocyanuric acid, obtained by oxidizing olefin bonds with peracid such as peracetic acid Linear aliphatic epoxy resins, such as cycloaliphatic epoxy resins. These may be used in combination of two or more kinds thereof may be used alone, which is liquid is preferred at ambient temperature (25 ° C.).

  0.01 mass%-1.5 mass% are preferable with respect to the whole epoxy resin, and, as for the content rate of surfactant, 0.05 mass%-1 mass% or less are more preferable. If the surfactant content is 0.01% by mass or more, a sufficient additive effect tends to be obtained, and if it is 1.5% by mass or less, the surface of the cured product is cured when the underfill material is cured. Therefore, it is difficult for the surfactant to ooze out, and the adhesive force tends not to decrease.

((F) ion trap agent)
The underfill material of the present disclosure has a viewpoint of improving the migration resistance, moisture resistance, and high-temperature storage characteristics of the ion trap agent as necessary within a range that does not impair the filling property and fluidity when applied to an electronic component device. Can be blended from
There is no restriction | limiting in particular as an ion trap agent, A conventionally well-known thing can be used, The hydrous oxide of the bismuth represented by the hydrotalcite represented by the following compositional formula (I) or the following compositional formula (II) preferable.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (I)
(In composition formula (I), 0 <X ≦ 0.5, and m represents a positive number.)
BiO _a (OH) _b (NO ₃ ) _c (II)
(In the composition formula (II), a, b and c are 0.9 ≦ a ≦ 1.1, 0.6 ≦ b ≦ 0.8 and 0.2 ≦ c ≦ 0.4, respectively.)

It is preferable that the content rate of an ion trap agent is 0.1 mass%-3.0 mass% with respect to the whole epoxy resin, More preferably, it is 0.3 mass%-1.5 mass%. The average particle size of the ion trapping agent is preferably 0.1 μm to 3.0 μm, and the maximum particle size is preferably 10 μm or less.
In addition, the compound represented by the said composition formula (I) is available as Kyowa Chemical Industry Co., Ltd. brand name DHT-4A as a commercial item. Moreover, the compound represented by the said composition formula (II) is available as IXE-500 (Toagosei Co., Ltd. brand name) as a commercial item.
If necessary, other anion exchangers can be blended as an ion trapping agent. There is no restriction | limiting in particular as an anion exchanger, A conventionally well-known thing can be used. Examples of the ion trapping agent include hydrated oxides such as magnesium, aluminum, titanium, zirconium, and antimony, and these can be used alone or in combination of two or more.

((G) curing accelerator)
Various curing accelerators can be blended with the underfill material of the present disclosure from the viewpoint of promoting the curing reaction between the epoxy resin and the curing agent.
The curing accelerator is not particularly limited as long as it accelerates the reaction between the epoxy resin and the curing agent, and conventionally known ones can be used. Examples of the curing accelerator include 1,8-diaza-bicyclo (5.4.0) undecene-7, 1,5-diaza-bicyclo (4.3.0) nonene, and 5,6-dibutylamino-1,8. Cycloamidine compounds such as diaza-bicyclo (5.4.0) undecene-7, tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2 -Methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4 , 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hy Roxymethylimidazole, 2,4-diamino-6- (2′-methylimidazolyl- (1 ′))-ethyl-s-triazine, imidazole compounds such as 2-heptadecylimidazole, trialkylphosphine such as tributylphosphine, dimethyl Organic phosphines such as dialkylarylphosphine such as phenylphosphine, alkyldiarylphosphine such as methyldiphenylphosphine, triphenylphosphine, triarylphosphine such as alkyl group-substituted triphenylphosphine, maleic anhydride, 1,4- Benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy Quinone compounds such as cis-1,4-benzoquinone and phenyl-1,4-benzoquinone, compounds having intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane and phenol resin, and derivatives thereof, Furthermore, phenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate may be used, and these may be used alone or in combination of two or more. Further, as a latent curing accelerator, a core-shell particle formed by coating a core of a compound having a solid amino group at normal temperature (25 ° C.) and a shell of a solid epoxy compound at normal temperature (25 ° C.) As a commercial product, Amicure (trade name, manufactured by Ajinomoto Co., Inc.), NovaCure (product made by Asahi Kasei Co., Ltd.), in which microencapsulated amine is dispersed in bisphenol A type epoxy resin and bisphenol F type epoxy resin Name) etc. can be used.

  Of these, imidazole derivatives are preferable from the viewpoint of a balance between curing acceleration and reliability, and 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4- which are imidazole derivatives having a phenyl group and a hydroxyl group as substituents. More preferred is Novacure (trade name, manufactured by Asahi Kasei Co., Ltd.) in which methyl-5-hydroxymethylimidazole and microencapsulated amine are dispersed in bisphenol A-type epoxy resin and bisphenol F-type epoxy resin to give a potential. More preferred are phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

  The content of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved, but a range of 0.2% by mass to 5% by mass with respect to the mass of all epoxy resins is preferable. A range of 0.5 mass% to 3 mass% is more preferable. If the content of the curing accelerator is 0.2% by mass or more, the addition effect of the curing accelerator is sufficiently exerted, and as a result, generation of voids when curing the underfill material can be suppressed, The warp reduction effect tends to be sufficient, and if it is 5% by mass or less, the storage stability tends to be excellent.

((H) coupling agent)
In the underfill material of the present disclosure, a coupling agent can be blended for the purpose of strengthening the adhesion at the interface between the epoxy resin and the inorganic filler, or the epoxy resin and the component member of the electronic component device. There is no restriction | limiting in particular in a coupling agent, A conventionally well-known thing can be used. Various coupling agents such as silane compounds having at least one selected from the group consisting of primary amino groups, secondary amino groups and tertiary amino groups, epoxy silanes, mercapto silanes, alkyl silanes, ureido silanes, vinyl silanes, etc. Examples include silane compounds, titanium compounds, aluminum chelates, and zirconium compounds.
Examples of these are vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Triethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropyltrimethoxy Silane, γ- (N, N-diethyl) aminopropyltrimethoxysilane, γ- (N, N-dibutyl) aminopropyltrimethoxysilane, γ- (N-methyl) anilinopropyltrimethoxysilane, γ- (N -Ethyl) anilinopropyltrimethoxysilane, γ- (N, N-dimethyl) aminopropyltriethoxysilane, γ- (N, N-diethyl) aminopropyltriethoxysilane, γ- (N, N-dibutyl) amino Propyltriethoxysilane, γ- (N-methyl) anilinopropyltriethoxysilane, γ- (N-ethyl) anilinopropyltriethoxysilane, γ- (N, N-dimethyl) aminopropylmethyldimethoxysilane, γ- (N, N-diethyl) aminopropylmethyldimethoxysilane, γ- (N, N-dibutyl) aminopropy Rumethyldimethoxysilane, γ- (N-methyl) anilinopropylmethyldimethoxysilane, γ- (N-ethyl) anilinopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ) Silane coupling agents such as ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, isopropyl Triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctane Rubis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate , Isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) And titanate coupling agents such as titanate. It may be used alone or in combination of two or more.

  It is preferable that the content rate of a coupling agent is 0.1 mass%-10 mass% with respect to the whole epoxy resin, More preferably, it is 1 mass%-5 mass%.

((I) Antioxidant)
An antioxidant can be blended in the underfill material of the present disclosure. A conventionally well-known thing can be used as antioxidant.
Phenol compound-based antioxidants include 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3,5 as compounds having at least one alkyl group at the ortho position of the phenol nucleus. -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis- (4-methyl-6-t-butylphenol), 3,9-bis [2- [3- (3-t-butyl -4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 4,4'-butylidenebis- (6- t-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), tetrakis [methylene-3- (3,5-di-tert-butyl-4) Hydroxyphenyl) propionate] methane, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionamide], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2, 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 4,6-bis (dodecylthiomethyl) -o-cresol, bis [3,5-di-t-butyl- 4-hydroxybenzyl (ethoxy) phosphinate] calcium, 2,4-1-bis [(octylthio) methyl] -o-cresol, 1,6-hexanediol-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10- Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4- Methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2,2′-methylenebis- (4- Ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tri Ethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tris (3,5-di-tert-butyl-4hydroxybenzyl) isocyanurate, diethyl [[3,5-bis ( 1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 2,5,7,8-tetramethyl-2- (4 ′, 8 ′, 12′-trimethyltridecyl) chroman-6-ol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like can be mentioned.
Organic sulfur compound-based antioxidants include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythrityl Tetrakis (3-laurylthiopropionate), ditridecyl-3,3′-thiodipropionate, 2-mercaptobenzimidazole, 4,4′-thiobis (6-tert-butyl-3-methylphenol), 2, 2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,6-bis (dodecylthiomethyl) -o-cresol, 2,4-1-bis [(Octylthio) methyl] -o-cresol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino 1,3,5-triazine.
Examples of amine compound antioxidants include N, N′-diallyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, octylated diphenylamine, 2,4-bis- (n- Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine and the like.
Among the amine compound-based antioxidants, as dicyclohexylamine, trade name D-CHA-T manufactured by Shin Nippon Rika Co., Ltd. is commercially available, and derivatives thereof include dicyclohexylamine ammonium nitrite, N, N -Di (3-methyl-cyclohexyl) amine, N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromo-cyclohexyl) amine and the like.
Phosphorus compound antioxidants include trisnonyl phenyl phosphite, triphenyl phosphite, bis [3,5-di-t-butyl-4-hydroxybenzyl (ethoxy) phosphinate] calcium, tris (2,4-di -T-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] -N, N-bis [2-{[2,4,8,10-tetrakis (1,1 dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphate Pin-6-yl] oxy} -ethyl] ethanamine, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1, , 2] dioxaphosphepin, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, and the like.
Antioxidants may be used alone or in combination of two or more. As specific examples of the antioxidant, there are compounds containing at least one of a phosphorus atom, a sulfur atom and an amine in the same molecule in addition to the phenolic hydroxyl group, but these compounds may be listed in duplicate. is there.

  It is preferable that the content rate of antioxidant is 0.1 mass%-10 mass% with respect to the whole epoxy resin, More preferably, it is 0.5 mass%-5 mass%.

((J) Organic solvent)
In the underfill material of the present disclosure, an organic solvent can be blended as necessary to reduce the viscosity. In particular, when a solid epoxy resin and a curing agent are used, an organic solvent is preferably blended in order to obtain a liquid underfill material.
The organic solvent is not particularly limited, and alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, ketone solvents such as acetone and methyl ethyl ketone, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, Glycol ether solvents such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate, lactone solvents such as γ-butyrolactone, δ-valerolactone, ε-caprolactone, dimethylacetamide, dimethyl Examples include amide solvents such as formamide, and aromatic solvents such as toluene and xylene. It may be used in combination of two or more. Among these, an organic solvent having a boiling point of 170 ° C. or higher is preferable from the viewpoint of avoiding bubble formation due to rapid volatilization when the underfill material is cured.

  The amount of the organic solvent is not particularly limited as long as it does not form bubbles when the underfill material is cured, but it is preferably 10% by mass or less with respect to the entire underfill material, and 5% by mass or less. More preferably.

(Other additives)
In the underfill material of the present disclosure, as other additives, a coloring agent such as a dye and carbon black, a diluent, a leveling agent, an antifoaming agent, and the like can be blended as necessary.

(Physical properties of underfill material)
The viscosity of the underfill material is not particularly limited. Among these, from the viewpoint of high fluidity, it is preferably 1 Pa · s to 100 Pa · s at 25 ° C., more preferably 3 Pa · s to 70 Pa · s. The viscosity of the underfill material is measured at 25 ° C. using an E-type viscometer (cone angle 3 °, rotation speed 10 rotations / minute).

  In addition, as an index of ease of filling when filling an underfill material between 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 0.3 Pa · s or less. It is preferable that it is 0.2 Pa · s or less. The viscosity of the underfill material at 110 ° C. is measured with a rheometer AR2000 (TA Instrument, aluminum cone 40 mm, shear rate 32.5 / sec).

  Further, the underfill material is a throttling index which is a ratio of a viscosity at a rotation speed of 1.5 rotations / minute measured at 25 ° C. using an E-type viscometer to a viscosity at a rotation speed of 10 rotations / minute [ (Viscosity at 1.5 revolutions / minute) / (Viscosity at 10 revolutions / minute)] is preferably 0.3 to 1.1, more preferably 0.4 to 1.0. Fillet formation property improves more as the change index is the said range. In addition, the viscosity and the change index of the underfill material can be set to a desired range by appropriately selecting the composition of the epoxy resin, the content of the inorganic filler, and the like.

(Physical properties of cured product)
In the present disclosure, a cured product of the underfill material used for measurement of glass transition temperature and thermal expansion coefficient by TMA and storage elastic modulus by DMA was obtained by heating the underfill material at 150 ° C. for 2 hours. Is.

The thermal expansion coefficient below the glass transition temperature measured by TMA (thermomechanical analysis) when the underfill material is a cured product is 30 ppm / ° C. or less, preferably 28 ppm / ° C. or less, preferably 26 ppm / ° C. or less. More preferably. If the thermal expansion coefficient below the glass transition temperature is 30 ppm / ° C. or less, the occurrence of bump cracks during reflow is suppressed, and the temperature cycle resistance is improved. The coefficient of thermal expansion below the glass transition temperature measured by TMA (thermomechanical analysis) may be 15 ppm / ° C. or higher.
The storage elastic modulus at 240 ° C. measured by DMA (dynamic viscoelasticity measurement) when the underfill material is a cured product is 0.10 GPa or less, preferably 0.09 GPa or less, and 0.08 GPa or less. More preferably, it is 0.07 GPa or less. If the storage elastic modulus at 240 ° C. is 0.10 GPa or less, generation of cracks in the solder resist during reflow is suppressed, and the temperature cycle resistance is improved. The storage elastic modulus at 240 ° C. measured by DMA (dynamic viscoelasticity measurement) may be 0.02 GPa or more.
The glass transition temperature measured by TMA (thermomechanical analysis) when the underfill material is a cured product is preferably 60 ° C to 150 ° C, more preferably 70 ° C to 140 ° C, and further preferably 70 ° C to 130 ° C or less. . If the glass transition temperature is 60 ° C. or higher, the bumps have high protection properties at high temperatures, and disconnection is unlikely to occur. Further, when the glass transition temperature is 150 ° C. or lower, the warpage at normal temperature (25 ° C.) tends not to increase.
The storage elastic modulus at 25 ° C. measured by DMA (dynamic viscoelasticity measurement) when the underfill material is a cured product is preferably 5 GPa to 10 GPa, and more preferably 5.5 GPa to 9.5 GPa. Preferably, it is 6 GPa to 9 GPa. If the storage elastic modulus at 25 ° C. is 5 GPa or more, the protection property of the bumps at a high temperature tends to be high, and disconnection is unlikely to occur. Further, when the elastic modulus at 25 ° C. is 10 GPa or less, the warpage at normal temperature (25 ° C.) tends not to increase.

The TMA can be measured using, for example, TA4000SA manufactured by TA Instruments. As a measurement condition, the temperature raising condition can be set to 5 ° C./min.
The DMA can be measured using, for example, Q800 manufactured by TA Instruments. As measurement conditions, the frequency can be 1 Hz, and the temperature rise condition can be 3 ° C./min.

(Manufacture of underfill materials)
The underfill material of the present disclosure can be manufactured by any method as long as the various components can be uniformly dispersed and mixed. As a general method, an underfill material is obtained by weighing components with a predetermined mixing ratio, mixing them using a raking machine, mixing roll, planetary mixer, etc., kneading, and defoaming as necessary. Can do.

<Electronic component device>
An electronic component device according to the present disclosure includes a wiring board, an electronic component disposed on the wiring board and electrically connected to the wiring board via a connection portion, and at least the wiring board and the electronic component. And a cured product of the underfill material of the present disclosure that seals the connection portion. The electronic component device of the present disclosure can be obtained by sealing at least a connection portion between the electronic component and the wiring board with the underfill material of the present disclosure. By sealing the electronic component with the underfill material, the electronic component device of the present disclosure is excellent in reliability such as temperature cycle resistance.
It is preferable that the connection part in an electronic component apparatus is a structure containing copper in order to ensure high electroconductivity.

Electronic component devices include lead frames, wired tape carriers, rigid wiring boards, flexible wiring boards, wiring boards such as glass and silicon wafers, active elements such as semiconductor chips, transistors, diodes, and thyristors, capacitors, and resistors. An electronic component device obtained by mounting electronic components such as passive elements such as a resistance array, a coil, and a switch and sealing necessary portions with the underfill material of the present disclosure can be given.
In particular, a semiconductor device in which a semiconductor device is flip-chip bonded to a wiring formed on a rigid wiring board, a flexible wiring board, or glass by bump connection is preferably sealed with the underfill material of the present disclosure. Specific examples of the flip-chip bonded semiconductor device include semiconductor devices such as flip-chip BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film).

The underfill material of the present disclosure is suitable as an underfill material for flip chip having excellent reliability. In the field of flip chip to which the underfill material of the present disclosure is particularly suitably applied, the material of the bump connecting the wiring board and the semiconductor element is not a conventional lead-containing solder, but a lead-free material such as Sn—Ag—Cu type. This is the field of flip chip semiconductor components using solder.
The connection part in an electronic component apparatus may be the structure which does not contain lead. The underfill material of the present disclosure can maintain good reliability even for a flip chip that is bump-bonded using lead-free solder that is physically brittle compared to conventional lead solder. Furthermore, it is suitable for an element whose semiconductor element size is 2 mm or more on the longer side, and a flip-chip connection in which the distance between the wiring board constituting the electronic component device and the bump connection surface of the semiconductor element is 200 μm or less. Therefore, it is possible to provide a semiconductor device that exhibits good fluidity and filling properties and is excellent in reliability such as moisture resistance and thermal shock resistance. In recent years, with the increase in the speed of semiconductor devices, interlayer dielectric films with low dielectric constants may be formed on the semiconductor devices. These low dielectric constant insulators have low mechanical strength and fail due to external stress. Is likely to occur. This tendency becomes more prominent as the semiconductor element becomes larger, and a reduction in stress due to the underfill material is required. The underfill material of the present disclosure is excellent for a flip-chip semiconductor device in which a semiconductor element having an interlayer insulating film having a dielectric constant of 3.0 or less is 2 mm or more on the longer side of the semiconductor element. Reliable.

<Method for manufacturing electronic component device>
Examples of a method for sealing an electronic component device using the underfill material of the present disclosure include a dispensing method, a casting method, and a printing method.
The underfill material of the present disclosure is suitably used for manufacturing an electronic component device in which an electronic component and a wiring board are electrically connected via a connection portion.
For example, the first method of manufacturing an electronic component device according to the present disclosure is provided on at least one of the surface of the electronic component that faces the wiring substrate and the surface of the wiring substrate that faces the electronic component. A supply step of supplying a fill material, and a connection step of connecting the electronic component and the wiring board via the connection portion and curing the underfill material. In the first method for manufacturing an electronic component device, the underfill material of the present disclosure can be used as an underfill material of a first supply method.
Further, the second electronic component device manufacturing method of the present disclosure includes a filling step of filling the gap between the connected electronic component and the wiring board with the underfill material of the present disclosure, and a curing step of curing the underfill material. Have. In the second method for manufacturing an electronic component device, the underfill material of the present disclosure can be used as an underfill material of a post-feed type.

  Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

  The evaluation methods of various properties and reliability of the underfill material performed in the examples are summarized below.

  The semiconductor element used for evaluation has a length of 25 mm, a width of 25 mm, and a thickness of 725 μm. The bumps are 30 μm high copper + 15 μm lead-free solder, the bump pitch is 150 μm, and the number of bumps is 25921. As the wiring board, E-705 (trade name, manufactured by Hitachi Chemical Co., Ltd.) having a length of 55 mm, a width of 55 mm, and a thickness of 1 mm was used. The solder resist was AUS703 (trade name, manufactured by Taiyo Ink Manufacturing Co., Ltd.) having a thickness of 15 μm.

  In an electronic component device, an underfill material is filled in a gap between a semiconductor element and a wiring board in a state where the semiconductor element and the wiring board are electrically connected via bumps, and cured at 150 ° C. for 2 hours. It was produced by. The curing conditions for various test pieces were also the same.

(1) Glass transition temperature TMA (thermomechanical analysis) is performed on the cured underfill material using TA4000SA manufactured by TA Instruments, and the intersection of tangent lines before and after the inflection point of the chart obtained is the glass transition temperature. It was. The heating rate was 5 ° C./min.
(2) Coefficient of thermal expansion TMA (thermomechanical analysis) was performed on the cured product of the underfill material using TA4000SA manufactured by TA Instruments Inc., and the slope obtained by connecting two points of 10 ° C and 30 ° C of the obtained chart Was divided by the length of the test piece to obtain a thermal expansion coefficient. The heating rate was 5 ° C./min.
(3) Storage elastic modulus DMA (dynamic viscoelasticity measurement) was performed on the cured product of the underfill material using Q800 (manufactured by TA Instruments), and a storage elastic modulus of 240 ° C. was obtained from the measurement results. The frequency was 1 Hz and the temperature elevation rate was 3 ° C./min.
(4) Solder resist crack An electronic component device that has undergone a thermal history of 1 minute or more at a temperature of 240 ° C. or higher three times is cut so that the bump portion can be observed, and a scanning electron microscope manufactured by Hitachi High-Technologies Corporation (device name) The presence or absence of solder resist cracks was observed with SU1510).
(5) Temperature cycle The electronic component device after performing the temperature cycle test with -55 ° C / 10 minutes and 125 ° C / 10 minutes as one cycle is an ultrasonic microscope (device name IS-350) manufactured by Insight Corporation. It was observed using, and the presence or absence of peeling of the hardened | cured material of an underfill material was observed. “> 1000” in Table 2 indicates that no peeling occurred at the end of 1000 cycles. <500 indicates that peeling occurred at the end of 500 cycles.

(Examples 1 to 5 and Comparative Examples 1 and 2)
As the epoxy resin of component (A), a liquid diepoxy resin (epoxy resin 1) having an epoxy equivalent of 160 g / eq obtained by epoxidizing bisphenol F, and a trifunctional having an epoxy equivalent of 95 g / eq obtained by epoxidizing aminophenol Liquid epoxy resin (epoxy resin 2), diepoxy resin having 140 g / eq epoxy equivalent obtained by epoxidizing naphthalenediol (epoxy resin 3), and liquid diepoxy resin having 128 g / eq epoxy equivalent obtained by epoxidizing alkyl diol (Epoxy resin 4) was used.
As the curing agent for component (B), 3,5-diethyltoluene-2,4-diamine having an active hydrogen equivalent of 45 g / eq was used.
As the inorganic filler of component (C), spherical silica having an average particle diameter of 1 μm was used.
As the flexibilizing agent for component (D), spherical silicone particles having an average particle diameter of 2 μm whose surface was modified with an epoxy group were used.
As a surfactant of the component (E), a silicone-modified epoxy resin that is a reaction product of an organosiloxane having a functional group that reacts with an epoxy group having a weight average molecular weight of 1000 and a bisphenol F type epoxy resin was used.
As the ion trapping agent of component (F), a bismuth ion trapping agent (trade name IXE-500, manufactured by Toagosei Co., Ltd.) was used.
2-Phenyl-4-methyl-5-hydroxymethylimidazole was used as a curing accelerator for component (G).
As a coupling agent for the component (H), γ-glycidoxypropyltrimethoxysilane was used.
(I) 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2, 4,8,10-Tetraoxaspiro [5.5] undecane was used.
As the organic solvent of the component (J), γ-butyrolactone was used.
Carbon black (trade name MA-100 manufactured by Mitsubishi Chemical Corporation) was used as a colorant.
Each of the above components is blended in the composition shown in Table 1 below, and kneaded and dispersed with a three-roller and a vacuum machine capable of reducing the pressure to produce the underfill materials of Examples 1 to 5 and Comparative Examples 1 and 2. did.

  In addition, the unit of the compounding quantity of each component in Table 1 is a mass part. In Table 1, “equivalent ratio” represents “equivalent number of curing agent (equivalent number of active hydrogen) / equivalent number of epoxy resin (equivalent number of epoxy group)”.

  Various evaluation results are summarized in Table 2 below.

In Examples 1 to 5, the glass transition temperature measured by TMA is 60 ° C. to 150 ° C., the thermal expansion coefficient is 30 ppm / ° C. or less, the storage elastic modulus at 25 ° C. measured by DMA is 5 GPa to 10 GPa, and 240 ° C. The storage elastic modulus was 0.10 GPa or less.
Although Comparative Example 1 having a storage elastic modulus at 240 ° C. of 0.40 GPa was excellent in temperature cycle resistance, solder resist cracks occurred. If the storage elastic modulus at high temperature is high, the underfill material cannot absorb the expansion of the solder at the reflow temperature and stress is applied to the solder resist.
In Comparative Example 2 having a coefficient of thermal expansion of 36 ppm / ° C., no solder resist crack was developed, but peeling was observed at a temperature cycle of 500 cycles. If the thermal expansion coefficient is large, the amount of expansion and contraction of the cured product of the underfill material due to the temperature cycle is large, and it is considered that the chip interface and the underfill material peeled during the contraction.

Claims (16)

(A) an epoxy resin, (B) a curing agent and (C) an inorganic filler,
The thermal expansion coefficient below the glass transition temperature measured by TMA (thermomechanical analysis) when cured is 30 ppm / ° C. or less, and the storage modulus at 240 ° C. measured by DMA (dynamic viscoelasticity measurement). An underfill material of 0.10 GPa or less.   The underfill material according to claim 1, wherein the glass transition temperature measured by TMA (thermomechanical analysis) when cured is 60 ° C to 150 ° C.   The underfill material according to claim 1 or 2, wherein a storage elastic modulus at 25 ° C measured by DMA (dynamic viscoelasticity measurement) when the cured product is obtained is 5 GPa to 10 GPa.   The underfill material according to any one of claims 1 to 3, further comprising (D) a flexibilizer.   The underfill material according to claim 1, further comprising (E) a surfactant.   The underfill material according to claim 1, further comprising (F) an ion trap agent.   The underfill material according to claim 1, further comprising (G) a curing accelerator.   The underfill material according to claim 1, further comprising (H) a coupling agent.   The underfill material according to any one of claims 1 to 8, further comprising (I) an antioxidant.   Furthermore (J) The underfill material of any one of Claims 1-9 which contains an organic solvent and the content rate of the said organic solvent is 10 mass% or less.   The underfill material according to claim 1, wherein the (B) curing agent is an aromatic amine compound. A wiring board;
An electronic component disposed on the wiring board and electrically connected to the wiring board via a connection portion;
The hardened | cured material of the underfill material of any one of Claims 1-11 which seals the connection part of the said wiring board and the said electronic component at least,
An electronic component device comprising:   The electronic component device according to claim 12, wherein the connection part does not contain lead.   The electronic component device according to claim 12, wherein the connection portion includes copper. An electronic component device manufacturing method in which an electronic component and a wiring board are electrically connected via a connecting portion,
The under of any one of Claims 1-11 on the surface of the side facing the said wiring substrate in the said electronic component, and at least one surface of the surface facing the said electronic component in the said wiring substrate. A supply process for supplying a fill material;
A connection step of connecting the electronic component and the wiring board via the connection portion and curing the underfill material. An electronic component device manufacturing method in which an electronic component and a wiring board are electrically connected via a connecting portion,
A filling step of filling the gap between the connected electronic component and the wiring board with the underfill material according to any one of claims 1 to 11,
And a curing step of curing the underfill material.