JP2006316250A - Liquid epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid epoxy resin composition suitable for sealing a semiconductor, having excellent adhesiveness to an element surface of a silicon chip (especially a photosensitive polyimide, a nitride film or an oxide film), affording a cured product having high moisture resistance and providing an excellent sealing material for high-temperature thermal shocks especially at ≥260°C reflow temperature and to provide a semiconductor device sealed with the composition. <P>SOLUTION: The liquid epoxy resin composition is characterized as follows. The composition consists essentially of a microcapsule type curing catalyst comprising (A) a liquid epoxy resin, (B) an aromatic amine curing agent containing ≥5 mass% of an aromatic amine compound represented by general formula (1) (wherein, R<SP>1</SP>to R<SP>3</SP>are each independently a group selected from a 1-6C monofunctional hydrocarbon group, a CH<SB>3</SB>S- and a C<SB>2</SB>H<SB>5</SB>S-) and (C) an acid anhydride. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is suitable for semiconductor sealing, has very good adhesion to the element surface (especially photosensitive polyimide, nitride film, oxide film) of the silicon chip, and gives a cured product with high moisture resistance. The present invention relates to a liquid epoxy resin composition that can be an excellent sealing material against a high-temperature thermal shock having a reflow temperature of 260 ° C. or higher, and a semiconductor device sealed with this composition.

  Along with the downsizing, weight reduction, and higher functionality of electrical equipment, semiconductor mounting methods have become mainstream from pin insertion type to surface mounting. 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, peeling at the interface between the sealing material and the die and the substrate, and cracks in the package when mounted on the substrate Has been close up.

  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 no problem in the past, also has a serious problem in that cracking occurs during reflow and separation from the chip interface and the substrate interface occurs. .

  As materials satisfying these requirements, liquid epoxy resins / alkyl-substituted aromatic diamine-based liquid sealing resins have been proposed (Patent Document 1: JP-A-9-176287, Patent Document 2: JP-A-9-176294). No. publication). This material is excellent in adhesion to a substrate, metal, solder resist, etc., and further excellent in reflow resistance and temperature cycle crack resistance, enabling a highly reliable package.

  However, the above resin system has a long curing time (150 ° C./3 hours), which is a problem from the viewpoint of package productivity. In addition, since the gelation time is long, there are disadvantages such as sedimentation of the filler, generation of surface cracks associated therewith, and short pot life. Further, in order to shorten the curing time, a study of a curing accelerator can be considered, and examples thereof include phenols and phenolic acids such as salicylic acid, but the pot life is short and workability is remarkably reduced. There were drawbacks.

JP-A-9-176287 JP-A-9-176294 JP-A-5-247179

  The present invention has been made in view of the above circumstances, can be cured in a shorter time than conventional, has excellent adhesion to the surface of a silicon chip, in particular, a photosensitive polyimide resin or a nitride film, and toughness. Gives an excellent cured product, and even if the reflow temperature is increased from about 240 ° C. to about 260 to 270 ° C., no defect occurs, and in a pressure cooker test (hereinafter referred to as PCT), 120 ° C./2.1 atm etc. A liquid epoxy resin composition that does not deteriorate even under high temperature and high humidity conditions, and can be used as a sealing material for a semiconductor device in which peeling and cracking do not occur even when the temperature cycle of −65 ° C./150° C. exceeds several hundred cycles, and this An object is to provide a semiconductor device sealed with a cured product of the composition.

  As a result of intensive studies to achieve the above object, the present inventor contains (A) a liquid epoxy resin, (B) 5% by mass or more of an aromatic amine compound represented by the following general formula (1). Aromatic amine curing agent,

（式中、Ｒ¹〜Ｒ³は独立に炭素数１〜６の一価炭化水素基、ＣＨ₃Ｓ−及びＣ₂Ｈ₅Ｓ−から選ばれる基である。）
（Ｃ）酸無水物を含有したマイクロカプセル型硬化触媒、及び好ましくは（Ｄ）無機質充填剤を含有する液状エポキシ樹脂組成物を用いること、この場合、特に、（Ａ）液状エポキシ樹脂のエポキシ当量と（Ｂ）芳香族アミン系硬化剤のアミン当量との当量比〔（Ａ）／（Ｂ）〕を０．７以上１．２以下とすることにより、シリコンチップの表面、特に感光性ポリイミド樹脂や窒化膜との密着性に優れ、ＰＣＴ（１２０℃／２．１ａｔｍ）などの高温多湿の条件下でも劣化せず、熱衝撃に対して優れており、特に大型ダイサイズの半導体装置の封止材として有効となり得ることを見出し、本発明をなすに至ったものである。

(Wherein, R ¹ to R ³ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, a CH ₃ S-, and C ₂ H ₅ S- from group selected.)
(C) Using a microcapsule-type curing catalyst containing an acid anhydride, and preferably (D) a liquid epoxy resin composition containing an inorganic filler, in this case, in particular, (A) the epoxy equivalent of the liquid epoxy resin And (B) the equivalent ratio of the amine equivalent of the aromatic amine curing agent [(A) / (B)] is 0.7 or more and 1.2 or less, so that the surface of the silicon chip, particularly the photosensitive polyimide resin Excellent adhesion to silicon and nitride films, does not deteriorate under high temperature and high humidity conditions such as PCT (120 ° C / 2.1 atm), and is excellent against thermal shock, especially for sealing large die size semiconductor devices It has been found that it can be effective as a material, and has led to the present invention.

  Furthermore, this liquid epoxy resin composition is obtained by using 5% by mass or more of the aromatic amine compound represented by the above general formula (1) as the aromatic amine curing agent (B). However, it has low viscosity and excellent workability, has excellent adhesion to the surface of the silicon chip, particularly photosensitive polyimide resin and nitride film, especially nitride film, and high temperature and high humidity such as PCT (120 ° C / 2.1 atm). It has been found that it does not deteriorate even under conditions and is excellent against thermal shock, and is particularly effective as a sealing material for a semiconductor device having a large die size.

  That is, the aromatic amine-based curing agent represented by the general formula (1) has a specific substituent compared to the conventional aromatic amine-based curing agent, so that it is cured relatively quickly. It has a long pot life and is excellent in mechanical properties, electrical properties, heat resistance properties and chemical resistance properties of the cured product. By using this curing agent, the surface of the silicon chip, particularly with the photosensitive polyimide resin or nitride film, The adhesiveness is excellent, the thermal shock resistance is remarkably improved, and excellent characteristics can be obtained even under high temperature and high humidity. Further, the aromatic amine curing agent of the present invention has a lower viscosity than conventional aromatic amine curing agents, so that the viscosity of the composition can be reduced, and workability and moldability are extremely excellent. It has been found that.

  The liquid epoxy resin composition of the present invention can shorten the curing time while maintaining storability. In addition, it gives a cured product with excellent adhesion to the surface of the silicon chip, particularly photosensitive polyimide resin and nitride film, and even if the reflow temperature after moisture absorption rises from around 240 ° C. to 260 to 270 ° C. Does not occur and does not deteriorate even under high-temperature and high-humidity conditions such as PCT (120 ° C / 2.1 atm), and peeling and cracking do not occur even if the temperature cycle of -65 ° C / 150 ° C exceeds several hundred cycles. A semiconductor device can be provided.

Hereinafter, the present invention will be described in more detail.
[(A) Liquid epoxy resin]
In the liquid epoxy resin composition of the present invention, (A) the liquid epoxy resin may be any epoxy resin that is liquid at room temperature and contains an epoxy group having three or less functional groups in one molecule. Those having a viscosity at 25 ° C. of 800 Pa · s or less, particularly 500 Pa · s or less are preferred. Specifically, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, naphthalene type epoxy resins, phenylglycidyl An ether etc. are mentioned, Among these, it is preferable to use a liquid epoxy resin at room temperature (25 degreeC). Moreover, the liquid epoxy resin of this invention can be used individually by 1 type or in combination of 2 or more types.

  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 ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and the monovalent hydrocarbon group is a methyl group. And alkyl groups such as ethyl group and propyl group, and 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 (2), 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.

[(B) Aromatic amine curing agent]
Next, the aromatic amine curing agent (B) used in the present invention contains an aromatic amine compound represented by the following general formula (1) in an amount of 5% by mass or more in the wholly aromatic amine curing agent. It is preferable that

（式中、Ｒ¹〜Ｒ³は独立に炭素数１〜６の一価炭化水素基、ＣＨ₃Ｓ−及びＣ₂Ｈ₅Ｓ−から選ばれる基である。）

(Wherein, R ¹ to R ³ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, a CH ₃ S-, and C ₂ H ₅ S- from group selected.)

Here, the monovalent hydrocarbon group of R ^{1 to} R ³ is preferably a group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and preferably 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 and hexyl group, vinyl groups, allyl groups, propenyl groups, butenyl groups, alkenyl groups such as hexenyl groups, phenyl groups, etc., and some or all of hydrogen atoms of these hydrocarbon groups And halogen-substituted monovalent hydrocarbon groups such as a fluoromethyl group, a bromoethyl group, and a trifluoropropyl group substituted with a halogen atom such as chlorine, fluorine, and bromine.

  Specific examples of the aromatic amine compound represented by the general formula (1) include diethyltoluenediamine, dimethylthiotoluenediamine, and dimethyltoluenediamine.

  The compounding amount of the aromatic amine compound represented by the general formula (1) is 5% by mass or more, preferably 10 to 100% by mass, more preferably 20 to 100% by mass, based on the entire aromatic amine curing agent. . When the aromatic amine compound represented by the general formula (1) is less than 5% by mass of the entire curing agent, the viscosity may increase, the adhesive force may decrease, or cracks may occur.

  Examples of aromatic amine curing agents other than the aromatic amine compound represented by the general formula (1) include aromatic diaminodiphenylmethane compounds such as 3,3′-diethyl-4,4′-diaminophenylmethane. 3,3 ′, 5,5′-tetramethyl-4,4′-diaminophenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminophenylmethane, 2,4-diaminotoluene An aromatic amine compound such as 1,4-diaminobenzene and 1,3-diaminobenzene is preferable.

  In the above aromatic amine-based curing agent, when it is solid at room temperature, the resin viscosity increases and workability is significantly deteriorated. Therefore, it is preferably melt-mixed with an epoxy resin in advance, and the specified blending amount described later Therefore, it is desirable to melt and mix in a temperature range of 70 to 150 ° C. for 1 to 2 hours. If the mixing temperature is less than 70 ° C, the aromatic amine curing agent may not be sufficiently compatible, and if the temperature exceeds 150 ° C, it may react with the epoxy resin and increase the viscosity. Also, if the mixing time is less than 1 hour, the aromatic 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 aromatic amine curing agent used in the present invention is the equivalent ratio of the liquid epoxy resin to the aromatic amine curing agent [(A) epoxy equivalent of the liquid epoxy resin / (B) aromatic amine. The amine equivalent of the system curing agent] is 0.7 to 1.2, preferably 0.7 to 1.1. More preferably, it is recommended to be in the range of 0.85 to 1.05. If the equivalent ratio is less than 0.7, unreacted amine groups remain, resulting in a decrease in the glass transition temperature, and the adhesion may be decreased. On the other hand, if it exceeds 1.2, the cured product becomes hard and brittle, and cracks may occur during reflow.

[(C) Microcapsule type curing catalyst]
In the present invention, a microcapsule type curing catalyst is blended as the component (C). This acts as a curing accelerator for the components (A) and (B), and the microcapsule type curing catalyst is a microcapsule catalyst containing an acid anhydride and has an average particle size of 0.5 to 10 μm. A maximum particle size of 50 μm or less, more preferably an average particle size of 2 to 5 μm and a maximum particle size of 20 μm or less, and the elution amount of the catalyst from the microcapsules in o-cresol is 30 ° C. It is preferable to blend a microcapsule type curing catalyst that is 70% by weight or more (that is, 70 to 100% by weight) of the total amount of catalyst contained in the microcapsules in 15 minutes.

  In this curing catalyst microcapsule, an acid anhydride is exemplified as the curing catalyst, specifically, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, pyromellitic. Acid dianhydride, maleated alloocimene, benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetrabisbenzophenone tetracarboxylic dianhydride, (3,4-dicarboxyphenyl) ether dianhydride Products, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, and the like.

  The microcapsule used in the present invention is a (meth) acrylic monomer, for example, an alkyl ester having 1 to 8 carbon atoms such as an acrylate ester, an itaconic acid ester or a crotonic acid ester, and the alkyl group of the alkyl ester is an allyl group. Monofunctional monomers such as styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, and ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene A polymer obtained by (co) polymerizing one kind selected from polyfunctional monomers such as bisphenol A di (meth) acrylate and methylenebis (meth) acrylamide alone or two or more kinds of monomers As a shell material, an acid anhydride is used as a catalyst in the polymer. Lee black those trapped in the capsule. In addition, in the said polymer, the polymer of a (meth) acrylate type monomer is preferable.

  There are various methods for producing the microcapsule-type curing catalyst containing the acid anhydride of the present invention. In order to produce microcapsules with high productivity and high sphericity, the suspension polymerization method is usually used. And can be produced by a conventionally known method such as an emulsion polymerization method. For example, JP-A-5-247179 discloses a method of microencapsulating a solid core material mainly composed of amines for epoxy resin curing agent with a radical polymerizable monomer containing an organic acid having a polymerizable double bond. Has been.

  In this case, in order to obtain high-concentration microcapsules from the molecular structure of a commonly used catalyst, the total amount of the monomers used with respect to 10 parts by mass of the curing catalyst is preferably about 10 to 200 parts by mass. More preferably, it is 10-100 mass parts, More preferably, it is 20-50 mass parts. If the amount is less than 10 parts by mass, it may be difficult to sufficiently contribute the potential. If the amount exceeds 200 parts by mass, the ratio of the catalyst is lowered, and in order to obtain sufficient curability, a large amount must be used. This may be economically disadvantageous. That is, the concentration of the curing catalyst contained in the microcapsule can be about 5 to 50% by mass, preferably about 10 to 50% by mass.

  As the microcapsules obtained by such a method, those having an average particle diameter of 0.5 to 10 μm and a maximum particle diameter of 50 μm or less are preferably used. More preferably, the average particle diameter is 2 to 5 μm and the maximum particle diameter is 20 μm or less. If the particle size of the microcapsules is too small, the specific surface area increases and the viscosity when mixed may increase. On the other hand, if the average particle size exceeds 10 μm, the dispersion in the resin becomes non-uniform, which may cause a decrease in reliability.

Incidentally, the average particle size, for example, a weight average value D ₅₀ (or median diameter) in particle size distribution measurement by laser diffraction method can be determined as such (hereinafter, the same).

  Moreover, it is preferable to use what has the following performance as said microcapsule. That is, 1 g of microcapsules containing acid anhydride are weighed, mixed with 30 g of o-cresol, and then left at 30 ° C. When the eluted catalyst is quantified by gas chromatography, the acid eluted from the microcapsule An anhydride having a content of 70% by mass or more of the total amount of acid anhydride contained in the microcapsule at 30 ° C. for 15 minutes is used. If it is less than 70% by mass, the curing time may take a long time, and the productivity may decrease. Desirably, the amount of elution is 75 mass% or more.

  The compounding amount of the microcapsules of the present invention is 0.5 to 20 parts by mass, particularly 1 to 15 parts by mass with respect to 100 parts by mass as a total of (A) liquid epoxy resin and (B) aromatic amine curing agent. Part. If the amount is less than 0.5 parts by mass, the curability may be lowered. If the amount exceeds 20 parts by mass, the curability is excellent, but the storability may be lowered.

  Further, an acid anhydride that is not microencapsulated may be added as a catalyst in combination with the above microencapsulated catalyst. In this case, the total amount of the acid anhydride contained in the microcapsule and the acid anhydride not microencapsulated is 100 mass of the total amount of (A) the liquid epoxy resin and (B) the aromatic amine curing agent. 0.5 to 20 parts by mass, preferably 0.5 to 15 parts by mass with respect to parts. If the amount is less than 0.5 parts by mass, the curability may be lowered. If the amount exceeds 20 parts by mass, the curability is excellent, but the storability may be lowered. In addition, it is preferable that the addition amount of the acid anhydride which is not microencapsulated is 1/10 or less of the total catalyst addition amount. If it exceeds 1/10, the curability is excellent, but the storage stability may be lowered.

[(D) Inorganic filler]
In the present invention, various known inorganic fillers (D) can be added for the purpose of reducing the expansion coefficient. Specific examples of the inorganic filler include fused silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, magnesia, magnesium silicate, and the like. Among them, spherical fused silica is desirable for reducing the viscosity.

  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 amino silanes such as -β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptosilane 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.

  When the composition of the present invention is used as a potting material, the inorganic filler preferably has an average particle diameter of 2 to 20 μm and a maximum particle diameter of 75 μm or less, particularly 50 μm or less. If the average particle size is less than 2 μm, the viscosity increases, and a large amount may not be filled. On the other hand, if the average particle size exceeds 20 μm, coarse particles increase, which may lead to a lead wire, that is, a void.

  In this case, the filling amount of the inorganic filler is 50 to 1,200 parts by weight, particularly 100 to 1,200, based on 100 parts by weight of the total amount of (A) liquid epoxy resin and (B) aromatic amine curing agent. A range of parts by mass is preferred. If the amount is less than 100 parts by mass, the coefficient of expansion is large and there is a risk of inducing cracks in the cooling test. If it exceeds 1,200 parts by mass, the viscosity becomes high and the fluidity may be lowered. A preferable viscosity in this case is 700 Pa · s or less, preferably 500 Pa · s or less at 25 ° C.

  When used as an underfill material, the inorganic filler has an average particle diameter with respect to the flip chip gap width (gap between the substrate and the semiconductor chip) in order to achieve both improved penetration and low linear expansion. Is preferably about 1/10 or less, and the maximum particle size is preferably ½ or less.

  As a compounding quantity of the inorganic filler in this case, it is preferable to mix | blend by 50-400 mass parts with respect to 100 mass parts of total amounts of (A) liquid epoxy resin and (B) aromatic amine type hardening | curing agent, More Preferably it mix | blends in 100-250 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. If it exceeds 400 parts by mass, the viscosity will increase and the thin film penetration may be reduced. A preferable viscosity in this case is 250 Pa · s or less, preferably 100 Pa · s or less at 25 ° C.

[Other additives]
The epoxy resin composition of the present invention may be blended with silicone rubber, silicone oil, liquid polybutadiene rubber, thermoplastic resin made of methyl methacrylate-butadiene-styrene, or the like for the purpose of reducing stress. Preferably, the alkenyl group of the alkenyl group-containing epoxy resin or phenol resin and the number of silicon atoms in one molecule represented by the following average composition formula (4) are 20 to 400, and the hydrogen atom (SiH group bonded to the silicon atom) ) Is preferably blended with a copolymer obtained by addition reaction with SiH groups of organopolysiloxane having 1-5.
H _a R ⁵ _b SiO _(4-ab) (4)
(Wherein R ⁵ is a substituted or unsubstituted monovalent hydrocarbon group, a is 0.01 to 0.1, b is 1.8 to 2.2, and 1.81 ≦ a + b ≦ 2.3. is there.)

The monovalent hydrocarbon group for R ⁵ is preferably a group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and is preferably a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert- Alkyl groups such as butyl group, hexyl group, octyl group and decyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group and hexenyl group, aryl groups such as phenyl group, xylyl group and tolyl group, benzyl Groups, phenylethyl groups, aralkyl groups such as phenylpropyl groups, etc., and fluorocarbon groups, bromoethyl groups, trifluoro, etc. in which some or all of the hydrogen atoms of these hydrocarbon groups are replaced by halogen atoms such as chlorine, fluorine, bromine, etc. Mention may be made of halogen-substituted monovalent hydrocarbon groups such as propyl groups.

  As the copolymer, the following structural formula (5) is preferable.

In the above formula (4), R ⁵ is the same as above, and R ⁶ is —CH ₂ CH ₂ CH ₂ —, —OCH ₂ —CH (OH) —CH ₂ —O—CH ₂ CH ₂ CH ₂ — or —O—CH ₂ CH ₂ CH ₂ —, wherein R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is an integer of 4 to 199, preferably 19 to 109, p is an integer of 1 to 10, and q is an integer of 1 to 10.

Stress is obtained by blending the above copolymer so that the amount of diorganopolysiloxane is 0 to 20 parts by mass, particularly 2 to 15 parts by mass with respect to the total of 100 parts by mass of the components (A) and (B). Can be further reduced. Here, the amount of diorganopolysiloxane is represented by the following formula.
Polysiloxane amount = (molecular weight of polysiloxane portion / molecular weight of component (E)) × added amount

  In the liquid epoxy resin composition of the present invention, if necessary, a carbon functional silane for improving adhesion, a pigment such as carbon black, a dye, an antioxidant, and other additives within a range not impairing the object of the present invention. Can be blended. However, in the present invention, it is preferable not to add an alkoxy-based silane coupling agent as a carbon-functional silane for improving adhesion other than the use as a surface treatment agent. In particular, when used as an underfill material, if an alkoxy-based silane coupling agent is blended even in a small amount, it may cause voids.

[Adjustment of liquid epoxy resin composition]
The liquid epoxy resin composition of the present invention is, for example, a liquid epoxy resin, an aromatic amine curing agent, a microcapsule, and if necessary, an inorganic filler and other additives at the same time or separately, and if necessary, heat treatment. While adding, it can be obtained by stirring, dissolving, mixing and dispersing. 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 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 500 Pa · s or less at 25 ° C. The molding method and molding conditions for this composition can be conventional methods, but preferably 100 to 120 ° C. for 0.5 hour or longer, and then 150 to 175 ° C. for 0.5 hour or longer. Heat oven cure under conditions. When heating at 100 to 120 ° C. is less than 0.5 hour, voids may occur after curing. Further, if the heating at 150 to 175 ° C. is less than 0.5 hours, sufficient cured product characteristics may not be obtained. In this case, the curing time is appropriately selected according to the heating temperature.

  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.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example.

[Examples 1 to 3, Comparative Examples 1 and 2]
Seven types of resin compositions were 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.
[Preservation]
The resin composition was stored at 25 ° C./60% RH, and half the time required to increase the viscosity by 20% under the above measurement conditions was defined as storage stability.
[Gelification time]
A 0.5 cc liquid resin composition was dropped onto a 150 ° C. hot plate and stirred with a spatula to determine the gelation time when the stringing was broken.
[Tg (glass transition temperature), CTE1 (expansion coefficient), CTE2 (expansion coefficient)]
Using a cured product test piece of 5 mm × 5 mm × 15 mm in which the resin composition was cured at 120 ° C./0.5 hours + 165 ° C./3 hours, TMA (thermomechanical analyzer) was used at a rate of 5 ° C. per minute. Tg when the temperature was raised was measured. 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.

[PCT peel test]
A polyimide-coated 10 mm × 10 mm silicon chip was placed on a 30 mm × 30 mm FR-4 substrate with a spacer of about 100 μm, and the composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C./3. It is cured under the conditions of time, peeled after being treated 5 times by IR reflow set at a maximum temperature of 265 ° C. after 30 ° C./65% RH / 192 hours, and further in an environment of PCT (121 ° C./2.1 atm) 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 with a spacer of about 100 μm, and the composition was intruded into the resulting gap, resulting in 120 ° C./0.5 hours + 165 ° C./3. It is cured under the conditions of time, and after 30 treatments with IR reflow set to a maximum temperature of 265 ° C after 30 ° C / 65% RH / 192 hours, -65 ° C / 30 minutes, 150 ° C / 30 minutes is one cycle. , 250 cycles, 500 cycles, 750 cycles, peeling after 1,000 cycles, cracks were confirmed.

(A) Liquid epoxy resin Epoxy resin a: Bisphenol F type epoxy resin (RE303S-L: Nippon Kayaku Co., Ltd.)
Epoxy resin b: trifunctional epoxy resin represented by the following formula (6) (Epicoat 630H: manufactured by Japan Epoxy Resin Co., Ltd.)

(B) Curing agent Curing agent a: diethyltoluenediamine (molecular weight = 178)
Curing agent b: dimethylthiotoluenediamine (molecular weight = 214.4)
Curing agent c: dimethyltoluenediamine (molecular weight = 150)
Curing agent d: Tetraethyldiaminophenylmethane (C-300S: manufactured by Nippon Kayaku Co., Ltd.)

(C) Curing catalyst Curing catalyst a: Microcapsules of benzophenone tetracarboxylic acid anhydride (BTDA: manufactured by Gulf Oil Co.), a polymer of methyl methacrylate containing 20% by mass of BTDA, and an average particle size The amount of the catalyst eluted from the microcapsule by treatment at 7 ° C. in o-cresol at 30 ° C. for 15 minutes is 87% by mass.
Curing catalyst b: benzophenone tetracarboxylic anhydride (BTDA: manufactured by Gulf Oil Co., Ltd.)
(D) Inorganic filler Spherical silica: Spherical silica having a maximum particle size of 24 μm and an average particle size of 6 μm (manufactured by Tatsumori Co., Ltd.)

Other additives Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (KBM403: manufactured by Shin-Etsu Chemical Co., Ltd.)
Carbon black: Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd.)
Copolymer: a copolymer obtained by an addition reaction between the alkenyl group of the alkenyl group-containing epoxy resin represented by the following formula (8) and the SiH group of the SiH group-containing organopolysiloxane represented by the following formula (7) ( Content of organopolysiloxane part = 81.5% by mass)

It is a schematic diagram of a flip chip type semiconductor device.

Explanation of symbols

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

Claims (7)

(A) Liquid epoxy resin (B) Aromatic amine curing agent containing 5% by mass or more of an aromatic amine compound represented by the following general formula (1)

(Wherein, R ¹ to R ³ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, a CH ₃ S-, and C ₂ H ₅ S- from group selected.)
(C) A liquid epoxy resin composition comprising a microcapsule-type curing catalyst containing an acid anhydride as an essential component.   (A) The addition amount of the microcapsule type curing catalyst containing an acid anhydride is 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the liquid epoxy resin and (B) the aromatic amine curing agent. The liquid epoxy resin composition according to claim 1, wherein   The (C) component microcapsule type curing catalyst has an average particle size of 0.5 to 10 μm, and the amount of catalyst elution from the microcapsules in o-cresol is 30 ° C. in 15 minutes. 3. The liquid epoxy resin composition according to claim 1, wherein the liquid epoxy resin composition is 70% by mass or more of the total amount of the catalyst contained.   The acid anhydride contained in the (C) component microcapsule is methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, pyromellitic dianhydride, maleated alloocimene, Benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetrabisbenzophenone tetracarboxylic dianhydride, (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-di The liquid epoxy resin composition according to any one of claims 1 to 3, which is an acid anhydride selected from carboxyphenyl) methane dianhydride and 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride. object.   (D) 50 to 1,200 parts by mass of inorganic filler as component (A) 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 of any one of Claims 1 thru | or 4.   A semiconductor device sealed with a cured product of the liquid epoxy resin composition according to claim 1.   A flip chip type semiconductor device in which a cured product of the liquid epoxy resin composition according to claim 1 is sealed as an underfill material.

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