JP2007176978A - Liquid epoxy resin composition for flip-chip semiconductor device and flip-chip semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid epoxy resin composition which has low viscosity and can give a cured product being very good in workability and adhesion to the surface of a silicon chip and high humidity resistance, and can serve as an excellent sealant against high-temperature thermal shock and to provide a flip-chip semiconductor device sealed with a cured product of the composition. <P>SOLUTION: The composition comprises a liquid epoxy resin, an aromatic amine-based curing agent, a silicone-modified epoxy resin of formula (1), and 50 to 400 pts.mass, per 100 pts.mass total of the above components, inorganic filler having an average particle diameter of about 1/10 or smaller and a maximum particle diameter of 1/2 or smaller in respect to the flip-chip gap width of a semiconductor device. In formula (1), R<SP>1</SP>is a hydrogen atom or a 1 to 4C alkyl group; R is an aliphatic-unsaturation-free unsubstituted or substituted monovalent hydrocarbon group; X is a bivalent organic group; k and m are positive numbers satisfying 0≤k≤100, 0<m≤100, and 0<k+m≤200; and n is an integer of 0 to 400. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is used for sealing a flip chip type semiconductor device, has a low viscosity, and has very good workability and adhesion to the surface of a silicon chip element (especially photosensitive polyimide, nitride film, oxide film). And a liquid epoxy resin composition for flip chip type semiconductor devices which can give a cured product with high moisture resistance and can be an excellent sealing material against a high-temperature thermal shock having a reflow temperature of 260 ° C. or more, and curing of this composition The present invention relates to a flip chip type semiconductor device sealed with an object.

  As electrical devices become smaller, lighter, and more functional, mounting methods from pin insertion type to surface mounting have become mainstream. In addition, along with the high integration of semiconductor elements, there are cases in which one side of the die size exceeds 10 mm, and the die size is increasing. In a semiconductor device using such a large die, the stress applied to the die and the sealing material increases during solder reflow, and peeling occurs at the interface between the sealing material and the die and the substrate, or the package cracks when mounted on the substrate. These issues have been highlighted.

  Furthermore, since lead-containing solder cannot be used in the near future, a number of lead substitute solders have been developed. Since this type of solder has a melting temperature higher than that of lead-containing solder, the reflow temperature is also examined at 260 to 270 ° C., and the conventional liquid epoxy resin composition sealing material is even more defective. Is expected. Thus, when the reflow temperature becomes high, the flip chip type package, which has not had any problems in the prior art, also generates cracks during reflow, separation from the chip interface and the substrate interface, and subsequent cooling cycles. When several hundred times or more have passed, a serious problem that a crack occurs in a resin, a substrate, a chip, or a bump portion has come to occur.

In addition, as a well-known document relevant to this invention, there exist the following.
JP-A-56-129246 Japanese Patent Laid-Open No. 2-170819 JP-A-4-41520 Japanese Patent Laid-Open No. 2-151621 JP-A-2005-146104

  The present invention has been made in view of the above circumstances, and provides a cured product having excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or a nitride film, and excellent toughness, and the reflow temperature is the conventional temperature. Even if the temperature rises from around 240 ° C to 260-270 ° C, no defects occur, and it does not deteriorate even under high temperature and high humidity conditions such as PCT (121 ° C / 2.1 atm), and the temperature cycle is -65 ° C / 150 ° C. Liquid epoxy resin composition for flip chip type semiconductor device that can be used as a sealing material for a semiconductor device in which peeling and cracking do not occur even if it exceeds several hundred cycles, and flip chip type semiconductor sealed with a cured product of this composition An object is to provide an apparatus.

  As a result of intensive studies to achieve the above object, the present inventor has (A) a liquid epoxy resin, (B) an aromatic amine-based curing agent, (C) a silicone represented by the following average composition formula (1). Liquid epoxy resin composition comprising, as essential components, a modified epoxy resin and (D) an inorganic filler having an average particle size of about 1/10 or less and a maximum particle size of 1/2 or less with respect to the flip chip gap width of the semiconductor device The flip chip type semiconductor device sealed with a cured product of the epoxy resin composition has excellent thermal moldability, and can be a cured product with excellent thermal shock resistance and moisture resistance reliability. It has been found that it has excellent thermal shock crack resistance and moisture resistance reliability.

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和基を含有しない非置換又は置換の一価炭化水素基であり、Ｘは二価の有機基である。ｋ、ｍは０≦ｋ≦１００、０＜ｍ≦１００、０＜ｋ＋ｍ≦２００を満たす正数であり、ｎは０〜４００を満たす整数である。）

Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and X is a divalent organic group. (K and m are positive numbers that satisfy 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, and n is an integer that satisfies 0 to 400.)

  That is, as the inorganic filler (D), the average particle size is about 1/10 or less with respect to the flip chip gap width (gap between the substrate and the semiconductor chip), and the maximum particle size is 1/2 with respect to the flip chip gap width. By using the following specific inorganic filler, the liquid epoxy resin composition of the present invention is excellent in injectability, and the workability is improved because no void is generated at the time of injection and curing. I found.

  In this case, in particular, the equivalent ratio [(A) / (B)] of (A) the epoxy equivalent of the liquid epoxy resin and (B) the amine equivalent of the aromatic amine curing agent is 0.7 or more and 1.2 or less. By doing so, it has excellent adhesion to the surface of the silicon chip, particularly photosensitive polyimide resin and nitride film, and does not deteriorate even under high temperature and high humidity conditions such as PCT (120 ° C / 2.1 atm), and is resistant to thermal shock. The inventors have found out that they are excellent and have come to make the present invention.

In addition, this applicant previously (A) liquid epoxy resin,
(B) an aromatic amine curing agent,
(C) a silicone-modified epoxy resin represented by the above average composition formula (1),
If necessary,
(D) A liquid epoxy resin composition containing an inorganic filler having an average particle size of ½ or less of the lead interval size of the semiconductor device and a maximum particle size of 2/3 or less of the lead interval size was proposed. (Japanese Patent Laid-Open No. 2005-146104: Patent Document 5), a suitable semiconductor device targeted by this composition is a cavity type semiconductor device or a COB type semiconductor device having a lead wire interval size of about 30 to 120 μm. . The present inventor has found that a highly reliable flip chip type semiconductor device can be obtained by blending the silicone-modified epoxy resin of the above formula (1) into the underfill material of the flip chip type semiconductor device. .

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和基を含有しない非置換又は置換の一価炭化水素基であり、Ｘは二価の有機基である。ｋ、ｍは０≦ｋ≦１００、０＜ｍ≦１００、０＜ｋ＋ｍ≦２００を満たす正数であり、ｎは０〜４００を満たす整数である。）
（Ｄ）半導体装置のフリップチップギャップ幅（基板と半導体チップとの隙間）に対して平均粒径が約１／１０以下、最大粒径が１／２以下である無機質充填剤：上記（Ａ），（Ｂ），（Ｃ）成分の総量１００質量部に対して５０〜４００質量部
を必須成分とすることを特徴とするフリップチップ型半導体装置用液状エポキシ樹脂組成物。
〔２〕 （Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との当量比〔（Ａ）液状エポキシ樹脂のエポキシ当量／（Ｂ）芳香族アミン系硬化剤のアミン当量〕が、０．７以上１．２以下である〔１〕の液状エポキシ樹脂組成物。
〔３〕 （Ｃ）シリコーン変性エポキシ樹脂の添加量が、（Ａ）液状エポキシ樹脂と（Ｂ）芳香族アミン系硬化剤との総量１００質量部に対し、０．１〜５０質量部であることを特徴とする〔１〕又は〔２〕の液状エポキシ樹脂組成物。
〔４〕 〔１〕〜〔３〕のいずれかに記載の液状エポキシ樹脂組成物の硬化物で封止したフリップチップ型半導体装置。 Accordingly, the present invention provides the following liquid epoxy resin composition for flip chip type semiconductor devices and flip chip type semiconductor devices.
[1] (A) Liquid epoxy resin,
(B) an aromatic amine curing agent,
(C) a silicone-modified epoxy resin represented by the following average composition formula (1):

Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and X is a divalent organic group. (K and m are positive numbers that satisfy 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, and n is an integer that satisfies 0 to 400.)
(D) An inorganic filler having an average particle size of about 1/10 or less and a maximum particle size of 1/2 or less with respect to the flip chip gap width (gap between the substrate and the semiconductor chip) of the semiconductor device: (A) A liquid epoxy resin composition for flip-chip type semiconductor devices, comprising 50 to 400 parts by mass as essential components with respect to 100 parts by mass of the total of components (B) and (C).
[2] Equivalent ratio of (A) liquid epoxy resin to (B) aromatic amine curing agent [(A) epoxy equivalent of liquid epoxy resin / (B) amine equivalent of aromatic amine curing agent] is 0 The liquid epoxy resin composition according to [1], which is 7 or more and 1.2 or less.
[3] The addition amount of (C) silicone-modified epoxy resin is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) liquid epoxy resin and (B) aromatic amine curing agent. The liquid epoxy resin composition according to [1] or [2].
[4] A flip chip type semiconductor device sealed with a cured product of the liquid epoxy resin composition according to any one of [1] to [3].

  The liquid epoxy resin composition for flip-chip type semiconductor devices of the present invention is excellent in workability, gives a cured product with excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or nitride film, and after moisture absorption Even if the reflow temperature of the conventional material rises from about 240 ° C. to about 260 to 270 ° C., no defect occurs, and it does not deteriorate even under high temperature and high humidity conditions such as PCT (120 ° C./2.1 atm). It is possible to provide a flip chip type semiconductor device in which peeling and cracking do not occur even when the temperature cycle of ℃ / 150 ℃ exceeds several hundred cycles.

  In the liquid epoxy resin composition for flip-chip type semiconductor devices of the present invention, the liquid epoxy resin (A) is preferably any epoxy resin that is liquid at room temperature and contains no more than three functional groups in one molecule. Can be used, but those having a viscosity at 25 ° C. of 800 Pa · s or less, particularly 500 Pa · s or less are preferable. Specifically, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable. , Naphthalene type epoxy resin, phenyl glycidyl ether, and the like. Among these, it is preferable to use an epoxy resin that is liquid at room temperature. Moreover, the liquid epoxy resin of this invention can be used individually by 1 type or in combination of 2 or more types. In the present invention, the viscosity is a value measured at 25 ° C. by a rotational viscometer.

Moreover, the epoxy resin of this invention may contain the epoxy resin shown by following Structural formula (2), (3) in the range which does not affect intrusion property.

Here, R ² is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20, preferably 1 to 10, and more preferably 1 to 3 carbon atoms, and examples of the monovalent hydrocarbon group include a methyl group and an ethyl group. And alkyl groups such as propyl group, alkenyl groups such as vinyl group and allyl group. X is an integer of 1 to 4, particularly 1 or 2.

In addition, when mix | blending the epoxy resin shown by said Formula (3), the compounding quantity is 25 mass% or more in all the epoxy resins, More preferably, it is 50 mass% or more, More preferably, it is 75 mass% or more. Recommended. If it is less than 25% by mass, the viscosity of the composition may increase or the heat resistance of the cured product may decrease. The upper limit may be 100% by mass.
Examples of the epoxy resin represented by the general formula (3) include RE600NM manufactured by Nippon Kayaku Co., Ltd.

  The total chlorine content in the liquid epoxy resin is preferably 1,500 ppm or less, more preferably 1,000 ppm or less. Moreover, it is preferable that the extraction water chlorine in 20 hours in the 50% epoxy resin density | concentration at 100 degreeC is 10 ppm or less. If the total chlorine content exceeds 1,500 ppm or the extracted water chlorine exceeds 10 ppm, the reliability of the semiconductor element, particularly the moisture resistance, may be adversely affected.

  Next, as the aromatic amine curing agent (B) used in the present invention, an aromatic diaminodiphenylmethane compound such as 3,3′-diethyl-4,4′-diaminophenylmethane, 3,3 ′, 5 is used. , 5'-tetramethyl-4,4'-diaminophenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminophenylmethane, 2,4-diaminotoluene, 1,4-diaminobenzene An aromatic amine such as 1,3-diaminobenzene is preferable. These may be used alone or in combination of two or more.

  Of the above aromatic amine curing agents, those that are liquid at room temperature can be blended as they are, but if they are blended as they are, the viscosity of the resin will increase and workability will be significantly reduced. It is preferable to melt and mix in a temperature range of 70 to 150 ° C. for 1 to 2 hours at a specified blending ratio described later. If the mixing temperature is less than 70 ° C, the amine curing agent may not be sufficiently compatible, and if the mixing temperature is higher than 150 ° C, it may react with the epoxy resin and increase the viscosity. Further, if the mixing time is less than 1 hour, the amine curing agent is not sufficiently compatible and may increase the viscosity, and if it exceeds 2 hours, it may react with the epoxy resin and increase the viscosity.

  The total amount of the amine curing agent used in the present invention is the equivalent ratio of the liquid epoxy resin and the amine curing agent [(A) epoxy equivalent of the liquid epoxy resin / (B) aromatic amine curing agent. It is recommended that the amine equivalent] be in the range of 0.7 to 1.2, preferably 0.7 to 1.1, and more preferably 0.85 to 1.05. If the blending molar ratio is less than 0.7, unreacted amino groups remain, and the glass transition temperature may be lowered or the adhesion may be lowered. On the other hand, if it exceeds 1.2, the cured product becomes hard and brittle, and cracks may occur during reflow or temperature cycling.

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｒは脂肪族不飽和基を含有しない非置換又は置換の一価炭化水素基であり、Ｘは二価の有機基である。ｋ、ｍは０≦ｋ≦１００、０＜ｍ≦１００、０＜ｋ＋ｍ≦２００を満たす正数であり、ｎは０〜４００を満たす整数である。） The liquid epoxy resin composition of the present invention uses (C) a silicone-modified epoxy resin represented by the following average composition formula (1) as a low stress agent.

Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and X is a divalent organic group. (K and m are positive numbers that satisfy 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, and n is an integer that satisfies 0 to 400.)

Here, R ¹ in the above formula is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group. R is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group Alkyl groups such as tert-butyl group, hexyl group, cyclohexyl group, octyl group and decyl group, aryl groups such as phenyl group, xylyl group and tolyl group, aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group Or a chloromethyl group, a bromoethyl group, a trifluoro group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as chlorine, fluorine, or bromine. 1 to 15 carbon atoms, such as a halogen-substituted monovalent hydrocarbon groups such as propyl group, are exemplified in particular 1-10 monovalent hydrocarbon group.

X is a divalent organic group, an alkylene group in which an oxygen atom may intervene, an arylene group, a group in which an alkylene group in which an oxygen atom may intervene and an arylene group are bonded, or a hydrogen atom of these groups Examples include a group partially or entirely substituted with a halogen atom, a hydroxyl group or the like, and those having 1 to 15 carbon atoms, particularly 2 to 10 carbon atoms are preferred. For example, the group shown below can be mentioned.

  K and m are positive numbers satisfying 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, but more preferable ranges are 0 ≦ k ≦ 10 from the viewpoint of low stress and thermal shock resistance. , 0 <m ≦ 10 and 0 <k + m ≦ 20. n is an integer satisfying 0 to 400, but a more preferable range is an integer of 8 to 100.

Specific examples of such silicone-modified epoxy resins include those shown below.

（式中、Ｒ¹は水素原子又は炭素数１〜４のアルキル基であり、Ｙは末端に二重結合を有する有機基である。ｋ、ｍは０≦ｋ≦１００、０＜ｍ≦１００、０＜ｋ＋ｍ≦２００を満たす正数である。）
で表されるエポキシ樹脂のＹの末端二重結合と、下記一般式（５）

（式中、Ｒは脂肪族不飽和基を含有しない非置換又は置換の一価炭化水素基、ｎは０≦ｎ≦４００の整数である。）
で示されるオルガノポリシロキサンのＳｉＨ基とを付加反応させることにより得ることができる。 The production method of the silicone-modified epoxy resin is the following average composition formula (4)

(In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is an organic group having a double bond at the terminal. K and m are 0 ≦ k ≦ 100, 0 <m ≦ 100. , 0 <k + m ≦ 200 is a positive number.)
Y-terminal double bond of the epoxy resin represented by the following general formula (5)

(In the formula, R is an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated group, and n is an integer of 0 ≦ n ≦ 400.)
It can obtain by carrying out addition reaction with SiH group of organopolysiloxane shown by these.

これらの中でも、特にアリル基が好ましい。 In the epoxy resin represented by the average composition formula (4), R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples thereof are the same as those described above for R ¹ . Y is an organic group having a double bond at the end, and is not particularly limited as long as it has a double bond at the end. Examples of the organic group having a double bond at the terminal include those containing an alkenyl group such as a vinyl group and an allyl group at the terminal, and an alkenyloxy group such as an allyloxy group. Examples thereof include those having a double bond at the end, and examples thereof include the following groups.

Among these, an allyl group is particularly preferable.

  K and m are positive numbers satisfying 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, but more preferable ranges are 0 ≦ k ≦ 10, 0 <m ≦ 10, 0 <k + m. It is a positive number satisfying ≦ 20.

（式中、Ｒ¹，ｋ，ｍは上記と同様である。） Specific examples of the epoxy resin represented by the formula (4) include those represented by the following formulas (4-i) to (4-iii).

(In the formula, R ¹ , k and m are the same as above.)

  The ratio (molar ratio) between the epoxy group in the epoxy resin represented by the above formula (4) and the organic group having a double bond at the end of Y is epoxy group: Y = 1: 2 to 100: 1, particularly It is preferably 1: 1 to 20: 1.

  In the organopolysiloxane represented by the general formula (5), R is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group. It is an integer of 0 ≦ n ≦ 400, particularly 8 ≦ n ≦ 100.

（式中、Ｍｅはメチル基、Ｐｈはフェニル基である。） Specific examples of such organopolysiloxanes include those represented by the following formula.

(In the formula, Me is a methyl group and Ph is a phenyl group.)

  Here, when the epoxy resin and the organosilicon compound are subjected to an addition reaction, each of the epoxy resin and the organosilicon compound may be used alone or in combination of two or more.

  In this addition reaction, the mixing ratio of the epoxy resin and the organosilicon compound is such that the molar ratio of the hydrogen atom (SiH group) bonded to the silicon atom in the organosilicon compound with respect to the Y terminal double bond in the epoxy resin is as follows. 0.2 to 1.0 mol / mol, particularly 0.4 to 0.95 mol / mol.

  Moreover, as a method of addition reaction, it can carry out according to a conventionally well-known addition reaction method. That is, in the addition reaction, conventionally known addition reaction catalysts such as platinum black, chloroplatinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, platinum Platinum catalysts such as bisacetoacetate, palladium catalysts such as tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium, rhodium catalysts such as chlorotris (triphenylphosphine) rhodium and tetrakis (triphenylphosphine) rhodium It is preferable to use a platinum group metal catalyst such as The addition amount of the addition reaction catalyst can be a catalyst amount, and the solution concentration is usually 20 to 60% by mass, and the catalyst concentration is 10 to 100 ppm in terms of platinum group metal mass with respect to the reaction product.

  The addition reaction is desirably performed in an organic solvent, and it is preferable to use an inert solvent such as benzene, toluene, or methyl isobutyl ketone as the organic solvent.

  Although the addition reaction conditions are not particularly limited, it is usually preferable to react at 60 to 120 ° C. for 30 minutes to 10 hours.

  The addition amount of the silicone-modified epoxy resin as component (C) is 0.1 to 50 parts by weight, particularly 5 for 100 parts by weight of the total amount of (A) liquid epoxy resin and (B) aromatic amine curing agent. -30 mass parts is preferable. If the addition amount is less than 0.1 parts by mass, improvement in thermal shock resistance and crack resistance may not be obtained. If the addition amount exceeds 50 parts by mass, the viscosity becomes high and workability may be hindered.

  As the inorganic filler (D) blended in the epoxy resin composition of the present invention, those usually blended in the epoxy resin composition can be used. Examples thereof include silicas such as fused silica and crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, glass fiber, and the like.

  In the present invention, the average particle size is about 1/10 or less, particularly 1/20 or less, and the maximum particle size is 1/2 or less, particularly with respect to the flip chip gap width (gap between the substrate and the semiconductor chip) of the semiconductor device. Use inorganic filler that is 1/3 or less. If the average particle size is larger than 1/10 of the flip chip gap width and the maximum particle size is larger than 1/2 of the flip chip gap width, the penetration may be reduced and voids may be generated.

  Here, in the present invention, the average particle diameter can be determined as, for example, a weight average value (or median diameter) by a laser light diffraction method or the like, and the maximum particle diameter can be similarly determined by a laser light diffraction method or the like. . Further, as a method for confirming that there is no particle having a particle size exceeding 1/2 of the lead interval size, for example, an inorganic filler and pure water are mixed at a ratio of 1: 9, and the aggregate is formed by ultrasonic treatment. A method is adopted in which the material is sufficiently broken and sieved with an opening filter having a half of the lead interval size to confirm that the inorganic filler does not remain on the filter.

  As a compounding quantity of an inorganic filler (D), 50-400 mass parts with respect to 100 mass parts of total amounts of (A) liquid epoxy resin, (B) aromatic amine type hardening | curing agent, and (C) silicone modified epoxy resin, More preferably, it is the range of 150-300 mass parts. If it is less than 50 parts by mass, the expansion coefficient is large, and there is a risk of inducing cracks in the cold test. Moreover, when it exceeds 400 mass parts, a viscosity will become high and there exists a problem which brings about the fall of thin film penetration | invasion property.

  In order to increase the bond strength between the resin and the inorganic filler, the inorganic filler is preferably blended in advance with a surface treatment with a coupling agent such as a silane coupling agent or a titanate coupling agent. As such a coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N Silane cups such as aminosilanes such as -β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptosilanes such as γ-mercaptosilane It is preferable to use a ring agent. Here, the blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

  Various additives can be further blended in the liquid epoxy resin composition of the present invention as necessary. For example, low stress agents such as thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, silicones, waxes such as carnauba wax, higher fatty acids, synthetic waxes, colorants such as carbon black, additives such as halogen trapping agents, etc. It can be added and blended.

  The liquid epoxy resin composition of the present invention includes, for example, a liquid epoxy resin, an aromatic amine curing agent, or a molten mixture of a liquid epoxy resin and an aromatic amine curing agent, a silicone-modified epoxy resin, and an inorganic filler, Depending on the conditions, other additives and the like can be obtained by stirring, dissolving, mixing, and dispersing at the same time or separately, if necessary, with heat treatment. The apparatus for mixing, stirring, dispersing and the like is not particularly limited, and a lykai machine, a three roll, a ball mill, a planetary mixer, a bead mill and the like equipped with a stirring and heating device can be used. Moreover, you may use combining these apparatuses suitably.

  In the present invention, the viscosity of the liquid epoxy resin composition used as the sealing material is preferably 1,000 Pa · s or less, particularly 10 to 800 Pa · s at 25 ° C. The molding method and molding conditions for this composition may be conventional methods, but preferably 100 to 120 ° C. for 0.5 hour or longer, particularly 0.5 to 2 hours, and then 130 to 250. Thermal oven curing is performed at a temperature of 0.5 ° C. for 0.5 hours or more, particularly 0.5 to 5 hours. When heating at 100 to 120 ° C. is less than 0.5 hour, voids may occur after curing. Further, if the heating at 130 to 250 ° C. is less than 0.5 hour, sufficient cured product characteristics may not be obtained.

  Here, as a flip chip type semiconductor device used in the present invention, for example, as shown in FIG. 1, for example, a semiconductor chip 3 is usually mounted on a wiring pattern surface of an organic substrate 1 via a plurality of bumps 2. The gap between the organic substrate 1 and the semiconductor chip 3 (the gap between the bumps 2) is filled with the underfill material 4 and the side portion thereof is sealed with the fillet material 5. The sealing material of the present invention is particularly effective when used as such an underfill material.

  Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention more specifically. However, the present invention is not limited to the following examples. In the following examples, Me represents a methyl group.

[Synthesis Example 1] Synthesis of Compound A 400 g of toluene in an 2 L four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, an allyl group-containing epoxy resin represented by the following formula (6) (epoxy Equivalent 310) 10 g was added, and azeotropic dehydration was performed for 2 hours in a nitrogen atmosphere. Thereafter, the system was cooled to 80 ° C., 1.00 g of platinum chloride catalyst was added, and a solution obtained by dissolving 48.5 g of an organosilicon compound represented by the following formula (7) in 194.1 g of toluene was dropped over 2 hours. did. The system was stirred for 6 hours while maintaining the system at 90 to 100 ° C., aged, and then cooled to room temperature. Thereafter, the solvent was distilled off under reduced pressure to obtain 56.2 g of the target silicone-modified epoxy resin (Compound A).

アリル基含有エポキシ樹脂組成
ｓ＝０、ｔ＝１ …５５モル％
ｓ＝１、ｔ＝１ …３５モル％
ｓ＝２、ｔ＝１ …１０モル％

Allyl group-containing epoxy resin composition s = 0, t = 1... 55 mol%
s = 1, t = 1 ... 35 mol%
s = 2, t = 1 ... 10 mol%

As a result of measuring ¹ H-NMR and IR of the obtained reaction product, ¹ H-NMR was -0.5-0.5, 3.6-3.9, 6.6-7.2, 8. A peak was shown at 0-8.2 ppm, and IR showed a peak derived from Si-Me in the vicinity of 1255 cm ⁻¹ . ²⁹ Si-NMR also showed a peak in the vicinity of 9.5 ppm. Thereby, it turned out that the compound A shown by the following average composition formula (8) was obtained.

(Compound A)

[Examples 1-4, Comparative Examples 1-3]
A resin composition was obtained by uniformly kneading the components shown in Table 1 with three rolls. The test shown below was done using these resin compositions. The results are shown in Table 2.

[viscosity]
The viscosity at 25 ° C. was measured at a rotation speed of 4 rpm using a BH type rotational viscometer.

[Tg (glass transition temperature), CTE1 (expansion coefficient), CTE2 (expansion coefficient)]
Using a cured product test piece of 5 mm × 5 mm × 15 mm, Tg was measured when the temperature was raised at a rate of 5 ° C. per minute by TMA (thermomechanical analyzer). Moreover, the expansion coefficient in the following temperature range was measured. The temperature range of CTE1 is 50 to 80 ° C, and the temperature range of CTE2 is 200 to 230 ° C.

[Adhesion test]
On a silicon chip coated with photosensitive polyimide, a frustoconical resin composition test piece having an upper surface diameter of 2 mm, a lower surface diameter of 5 mm, and a height of 3 mm is placed, and 120 ° C. for 0.5 hour, and then 165 ° C. for 3 hours Cured for hours. After curing, the shear strength of the obtained specimen was measured and used as the initial value. Further, the cured test piece was absorbed with PCT (121 ° C./2.1 atm) for 336 hours, and then the adhesive strength was measured. In any case, the number of test pieces was five, and the average value was expressed as adhesive strength.

[PCT peel test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate using a spacer of about 100 μm, and the resin composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C. / Curing for 3 hours, 30 ° C / 65% RH / 192 hours later, IR reflow set to maximum temperature of 265 ° C, stripping after 5 treatments, and PCT (121 ° C / 2.1 atm) environment The peeling after 336 hours was confirmed by C-SAM (manufactured by SONIX).

[Thermal shock test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate using a spacer of about 100 μm, and the resin composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C. / Curing for 3 hours, 30 cycles of IR reflow set to maximum temperature of 265 ° C after 30 ° C / 65% RH / 192 hours, then -65 ° C / 30 minutes, 150 ° C / 30 minutes for one cycle And peeling and cracking after 250,500,750,1000 cycles were confirmed.

[Invasion test]
Two glass plates of 30 mm × 70 mm were used, a gap was installed using a spacer of about 60 μm, and the resin composition penetration into the gap generated at 120 ° C. was confirmed. Those that penetrated 50 mm or more were marked with ◯, and those that did not penetrate were marked with ×.

芳香族アミン系硬化剤ａ：４，４’−ジアミノ−３，３’−ジエチルジフェニルメタン（
日本化薬（株）製）
Ｃ−３００Ｓ：テトラエチルジアミノフェニルメタン（日本化薬（株）製）
無機質充填剤ａ：最大粒径２４μｍ、平均粒径６μｍの球状シリカ（（株）龍森製）
無機質充填剤ｂ：最大粒径５３μｍ、平均粒径１０μｍの球状シリカ（（株）龍森製）
シランカップリング剤：ＫＢＭ４０３、γ−グリシドキシプロピルトリメトキシシラン（
信越化学工業（株）製）
カーボンブラック：デンカブラック（電気化学工業（株）製） RE303S-L: Bisphenol F type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
Epicoat 630H: Trifunctional epoxy resin represented by the following formula (Japan Epoxy Resin
(Made by Co., Ltd.)

Aromatic amine curing agent a: 4,4′-diamino-3,3′-diethyldiphenylmethane (
Nippon Kayaku Co., Ltd.)
C-300S: Tetraethyldiaminophenylmethane (manufactured by Nippon Kayaku Co., Ltd.)
Inorganic filler a: spherical silica having a maximum particle size of 24 μm and an average particle size of 6 μm (manufactured by Tatsumori)
Inorganic filler b: spherical silica having a maximum particle size of 53 μm and an average particle size of 10 μm (manufactured by Tatsumori)
Silane coupling agent: KBM403, γ-glycidoxypropyltrimethoxysilane (
(Shin-Etsu Chemical Co., Ltd.)
Carbon black: Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.)

It is sectional drawing which shows an example of the flip chip type semiconductor device using the sealing material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic substrate 2 Bump 3 Semiconductor chip 4 Underfill material 5 Fillet material

Claims (4)

(A) Liquid epoxy resin,
(B) an aromatic amine curing agent,
(C) a silicone-modified epoxy resin represented by the following average composition formula (1):

Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R is an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated group, and X is a divalent organic group. (K and m are positive numbers that satisfy 0 ≦ k ≦ 100, 0 <m ≦ 100, and 0 <k + m ≦ 200, and n is an integer that satisfies 0 to 400.)
(D) An inorganic filler having an average particle size of about 1/10 or less and a maximum particle size of 1/2 or less with respect to the flip chip gap width (gap between the substrate and the semiconductor chip) of the semiconductor device: (A) A liquid epoxy resin composition for flip-chip type semiconductor devices, comprising 50 to 400 parts by mass as essential components with respect to 100 parts by mass of the total of components (B) and (C).   Equivalent ratio of (A) liquid epoxy resin and (B) aromatic amine curing agent [(A) epoxy equivalent of liquid epoxy resin / (B) amine equivalent of aromatic amine curing agent] is 0.7 or more The liquid epoxy resin composition according to claim 1, which is 1.2 or less.   (C) The addition amount of the silicone-modified epoxy resin is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of (A) liquid epoxy resin and (B) aromatic amine curing agent. The liquid epoxy resin composition according to claim 1 or 2. A flip chip type semiconductor device sealed with a cured product of the liquid epoxy resin composition according to claim 1.

Images