JP2010077234A - Liquid epoxy resin composition and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured product that can be cured at a low temperature and in a short time compared with conventional ones, has excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or a nitride film, and has excellent toughness. A liquid epoxy resin composition for providing a semiconductor device and a semiconductor device sealed with a cured product of the composition are provided.
SOLUTION: (A) Liquid epoxy resin, (B) Aromatic amine curing agent, (C) The following general formula (1) and / or (2) as a curing accelerator
R ^1- [COO—CH (CH ₃ ) —OR ² ] _n (1) (wherein n is a positive number, R ¹ is an n-valent organic group, and R ² is a monovalent organic group) R ¹ and R ² may be the same or different from each other.)
H— [OCO—R ³ —COO—CH (CH ₃ ) —OR ⁴ —O—CH (CH ₃ )] _m —H (2) (wherein m is a positive number and R ³ and R ⁴ Are divalent organic groups, which may be the same or different from each other.) A liquid epoxy resin composition characterized by comprising as an essential component a compound represented by:
[Selection figure] None

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 at 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, with the increase in functionality of semiconductor elements, there are cases where one side of the die size exceeds 10 mm, and the die size has been increased. 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 not had any problems in the past, has a serious problem that cracks occur at the time of reflow and peeling from the chip interface and the substrate interface occurs. It came to happen.

  As a material satisfying these requirements, a liquid epoxy resin / alkyl-substituted aromatic diamine-based liquid sealing resin has been proposed (JP-A-9-176287: Patent Document 1, JP-A-9-176294: Patent). Reference 2). 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. In addition, in order to reduce the curing temperature and shorten the curing time, it is conceivable to examine a curing accelerator, and examples thereof include phenols and phenolic acids such as salicylic acid. There were drawbacks such as significantly lowering the.

JP-A-9-176287 JP-A-9-176294

  The present invention has been made in view of the above circumstances, and can be cured at a low temperature and in a short time as compared with the prior art, has excellent adhesion to the surface of a silicon chip, particularly a photosensitive polyimide resin or a nitride film, and is tough. High quality and high humidity conditions such as PCT (120 ° C / 2.1 atm) are obtained even when the reflow temperature is increased from about 240 ° C to about 260-270 ° C. Liquid epoxy resin composition that can be used as a sealing material of a semiconductor device that does not deteriorate even under a temperature of −65 ° C./150° C. An object of the present invention is to provide a semiconductor device encapsulated in the process.

  As a result of intensive studies to achieve the above object, the present inventor has (A) liquid epoxy resin, (B) aromatic amine-based curing agent, and (C) general formulas (1) and (2). It is preferable to use a liquid epoxy resin composition containing (D) an inorganic filler, and in this case, in particular, (A) the epoxy equivalent of the liquid epoxy resin and (B) an aromatic amine. By setting the equivalent ratio [(A) / (B)] with the amine equivalent of the system curing agent to 0.7 or more and 1.2 or less, adhesion to the surface of the silicon chip, particularly to the photosensitive polyimide resin or nitride film It does not deteriorate even under high-temperature and high-humidity conditions such as PCT (120 ° C / 2.1 atm), is excellent against thermal shock, and can be particularly effective as a sealing material for large die size semiconductor devices. Heading, make the present invention And it has reached.

Accordingly, the present invention provides (A) a liquid epoxy resin, (B) an aromatic amine curing agent, (C) a curing accelerator represented by the following general formula (1) or (2)
R ^1- [COO-CH (CH ₃ ) -OR ² ] _n (1)
(In the formula, n is a positive number, R ¹ is an n-valent organic group, R ² is a monovalent organic group. R ¹ and R ² may be the same or different from each other.)
H- [OCO-R ³ -COO-CH (CH ₃ ) -OR ⁴ -O-CH (CH ₃ )] _m -H (2)
(In the formula, m is a positive number, R ³ and R ⁴ are divalent organic groups, and may be the same or different from each other.)
And a semiconductor device sealed with a cured product of the liquid epoxy resin composition. Furthermore, a flip chip type semiconductor device in which a cured product of the liquid epoxy resin composition is sealed as an underfill material is provided.

  The liquid epoxy resin composition of the present invention can be cured at a low temperature while maintaining storability, and can shorten the curing time. 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.

(A) Liquid Epoxy Resin In the liquid epoxy resin composition of the present invention, the liquid epoxy resin of component (A) is preferably an epoxy resin that is liquid at room temperature and contains an epoxy group having 3 or less functional groups in one molecule. Any material 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. An epoxy resin, a naphthalene type epoxy resin, a phenyl glycidyl 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 mixture 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 (3), (4) in the range which does not affect intrusion property.

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

  In the above aromatic amine-based curing agent, when it is solid at room temperature, the resin viscosity increases and workability is significantly deteriorated, so it is preferable to melt and mix with the 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 blending amount of the aromatic amine curing agent used in the present invention is the 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 preferably 0.7 or more and 1.2 or less, particularly preferably 0.7 or more and 1.1 or less. If the equivalence 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.

(C) Curing accelerator The curing accelerator of the component (C) used in the present invention is a compound represented by the general formula (1) and / or (2).
R ^1- [COO-CH (CH ₃ ) -OR ² ] _n (1)
In the formula, n is a positive number, specifically 1 to 5, preferably 1 to 3. R ¹ is an n-valent organic group, specifically, an alkyl group having 1 to 15 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or a C ^{1 to} 15 carbon group such as a methylene group, an ethylene group, or a butylene group. Examples include an arylene group such as an alkylene group and a phenylene group, a cyclohexylene group, an ethylene glycol group, and a propylene glycol group. R ² is a monovalent organic group such as an alkyl group having 1 to 15 carbon atoms such as a methyl group, an ethyl group or a propyl group, an aryl group such as a phenyl group, a xylyl group or a biphenyl group, a vinyl group or an allyl group. An alkenyl group etc. are mentioned. R ¹ and R ² may be the same as or different from each other. )

H- [OCO-R ³ -COO-CH (CH ₃ ) -OR ⁴ -O-CH (CH ₃ )] _m -H (2)
In formula, m is a positive number, Preferably it is 1-20, More preferably, it is 1-10. Specifically, m is determined so that the molecular weight of (2) is 200 to 3000, preferably 500 to 2500. R ³ and R ⁴ are divalent organic groups, specifically, alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group, butylene group, arylene groups such as phenylene group, cyclohexylene group, An ethylene glycol group, a propylene glycol group, etc. are mentioned. R ³ and R ⁴ may be the same or different from each other.

The curing accelerators represented by the above general formulas (1) and (2) can be obtained by a reaction between carboxylic acids and a vinyl ether compound. For example, the compound (1) can be obtained by the following reaction.
R ^1- (COOH) _n + nR ² -O-CH = CH ₂ → R ^1- [COO-CH (CH ₃ ) -OR ² ] _n

The compound (2) can be obtained by the following reaction.
mR ^1- (COOH) ₂ + mH ₂ C = CH-OR ⁴ -O-CH = CH ₂ → H- [OCO-R ³ -COO-CH (CH ₃ ) -OR ⁴ -O-CH (CH ₃ ) ] _m -H

  Carboxylic acids include benzoic acid, isophthalic acid, isophthalic acid, terephthalic acid, hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, merit acid, toluic acid, xylic acid, hemelic acid, Examples thereof include cinnamic acid, salicylic acid, creosote acid, CIC acid, maleic acid, itaconic acid, adipic acid, acetic acid, acrylic acid, isocyanuric acid, and other carboxyl group-containing polybutadiene. As vinyl ether compounds, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, octadecyl vinyl ether, allyl vinyl ether, hydroxyethyl vinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether And vinyl ethers containing cyclohexanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, and the like.

  The above carboxylic acids are highly reactive with epoxy groups, and when added directly to an epoxy resin, low-temperature curing and short-time curing are possible, but the usable time of the resin is very short. In the present invention, by protecting the carboxylic acid with vinyl ether, it is possible to suppress the activity of the acid in the storage state, and when curing the resin, the curing accelerator causes thermal dissociation of the vinyl ether to generate a carboxyl group and cure. In order to promote this, it is possible to cure at low temperature and for a short time.

  To suppress the activity of the carboxylic acids at low temperatures. There is also a method in which a carboxylic acid is a core-shell type microcapsule made of a thermoplastic resin such as polymethacrylic acid, but the distance between die substrates of flip chip type semiconductor devices in recent years is mainly several tens μm or less, so that The particle size needs to be several μm or less in order not to impede the fluidity of the resin. However, when microcapsules of such a size are made, the potential for use as a curing accelerator is lowered and the pot life of the resin is reduced. Therefore, it is not preferable.

  In this invention, the compounding quantity of a hardening accelerator (C) is 0.05-20 mass parts with respect to 100 mass parts of total amounts of (A) liquid epoxy resin and (B) aromatic amine type hardening | curing agent, Desirably Is preferably 0.05 to 10 parts by mass. If it is 0.05 parts by mass or less, the curing accelerating property may be lowered, and if it exceeds 20 parts by mass, the properties of the cured product are lowered.

Other Additives In the present invention, various inorganic fillers known in the art can be added to the inorganic filler (D) for the purpose of reducing the expansion coefficient. Specific examples of the inorganic filler include fused silica, crystalline silica, alumina, boron nitride, ticker aluminum, ticker silicon, magnesia, magnesium silicate, aluminum 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 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.

  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 is high and a large amount may not be filled. On the other hand, if the average particle size is more than 20 μm, coarse particles increase, which may lead to voids in the lead wire.

  In this case, the filling amount of the inorganic filler is preferably in the range of 100 to 1,200 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. If it is less than 100 parts by mass, the expansion coefficient is large, and there is a risk of inducing cracks in the cold test. If it exceeds 1,200 parts by mass, the viscosity becomes high and the fluidity may be lowered.

  When used as an underfill material, the inorganic filler has an average particle size relative 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. It is preferable that the diameter is about 1/10 or less and the maximum particle diameter is 1/2 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 agents, 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.

  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 a hydrogen atom bonded to the silicon atom (SiH group) ) Is preferably blended with a copolymer obtained by addition reaction with SiH groups of organopolysiloxane having 1-5.

H _a R ⁶ _b SiO _{(4-ab) / 2} (5)
(Wherein R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group, a is 0.01 to 0.1, b is 1.8 to 2.2, and 1.81 ≦ a + b ≦ 2.3. .)

The monovalent hydrocarbon group for R ⁶ preferably has 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, or tert-butyl group. , Alkyl groups such as 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 group and phenyl group Fluoromethyl group, bromoethyl group, trifluoropropyl group, etc. in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine, fluorine, bromine, etc. And halogen-substituted monovalent hydrocarbon groups.
As the above-mentioned copolymer, those of the following structural formula (6) are particularly desirable.

In the above formula, 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 —, and 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 99, p is an integer of 1 to 10, and q is an integer of 1 to 10.

  The stress is further reduced by blending the above copolymer so that the diorganopolysiloxane unit is contained in an amount of 0 to 20 parts by mass, particularly 2 to 15 parts by mass with respect to 100 parts by mass of the liquid epoxy resin (A). be able to.

  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.

  The liquid epoxy resin composition of the present invention is, for example, a liquid epoxy resin, an aromatic amine-based curing agent, a curing accelerator, and if necessary, an inorganic filler and other additives simultaneously or separately, and if necessary, heat treatment 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 10 to 800 Pa · s at 25 ° C. The molding method and molding conditions of this composition may be conventional methods, but preferably 100 to 110 ° C. for 0.2 hours or longer, particularly 0.2 to 0.5 hours, and then 120 Heat oven cure is performed under conditions of ˜250 ° C. and 0.5 hours or more, particularly 0.5 to 5 hours. When heating at 100 to 110 ° C. is less than 0.2 hours, voids may occur after curing. Further, if the heating at 120 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.

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

[Examples 1-4, Comparative Examples 1-3]
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.
In addition, the following were used as a hardening accelerator used for this invention.

[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 specimen of 5 mm × 5 mm × 15 mm in which the resin composition was cured under the conditions of 110 / 0.5 hours + 120 / 2.0 hours, TMA (thermomechanical analyzer) was used at a rate of 5 ° C. per minute. The 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.

[Adhesion test]
On a silicon chip coated with photosensitive polyimide, a resin composition test piece in the shape of a truncated cone having a diameter of 2 mm on the upper surface, a diameter of 5 mm on the lower surface, and a height of 3 mm is placed and cured for 110 / 0.5 hours + 120 / 2.0 hours. I let you. 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 generated gap for 110 / 0.5 hours + 120/2. Peeling after curing for 5 hours with IR reflow set at maximum temperature of 265 ° C after 30 ° C / 65% RH / 192 hours after curing at 0 ° C, and further in 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 generated gap for 110 / 0.5 hours + 120/2. Curing was performed under the conditions of 0 hours, and after 30 treatments with IR reflow set to a maximum temperature of 265 ° C. after 30 ° C./65% RH / 192 hours, a cycle of −65 ° C./30 minutes and 150 ° C./30 minutes was performed. And peeling and cracking after 250,500,750,1000 cycles were confirmed.

(A) Liquid epoxy resin epoxy resin a: bisphenol F type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE303S-L)
Epoxy resin b: trifunctional epoxy resin represented by the following formula (7) (Japan Epoxy Resin Co., Ltd., Epicoat 630H)

(B) Aromatic amine curing agent Aromatic amine curing agent A: Diethyldiaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA)
Aromatic amine curing agent B: Tetraethyldiaminophenylmethane (Nippon Kayaku Co., Ltd., C-300S)

(C) Curing accelerator Curing accelerator A: Benzoic acid-vinyl ether adduct C ₆ H ₅ COOCH (CH ₃ ) OC ₃ H ₇
Curing accelerator B: adipic acid-vinyl ether copolymer
H- [OCO (CH ₂ ) ₄ COOCH (CH ₃ ) O (CH ₂ ) ₄ OCH (CH ₃ )] _m -H
(However, m is a number with an average molecular weight of 2000.)

(D) Inorganic filler: spherical silica having a maximum particle size of 50 μm and an average particle size of 10 μm

Other additive copolymer: silicone-modified epoxy resin comprising an addition reaction product of a compound of the following formula (8) and a compound of the following formula (9)

シランカップリング剤：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、ＫＢＭ４０３）
カーボンブラック：デンカブラック（電気化学工業（株）製）

Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403)
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 (5)

(A) Liquid epoxy resin,
(B) an aromatic amine curing agent,
(C) The following general formula (1) and / or (2) as a curing accelerator
R ^1- [COO-CH (CH ₃ ) -OR ² ] _n (1)
(In the formula, n is a positive number, R ¹ is an n-valent organic group, R ² is a monovalent organic group. R ¹ and R ² may be the same or different from each other.)
H- [OCO-R ³ -COO-CH (CH ₃ ) -OR ⁴ -O-CH (CH ₃ )] _m -H (2)
(In the formula, m is a positive number, R ³ and R ⁴ are divalent organic groups, and may be the same or different from each other.)
A liquid epoxy resin composition comprising a compound represented by the formula:   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 and 1 The liquid epoxy resin composition according to claim 1, which is .2 or less.   The (C) curing accelerator is 0.05 parts by mass to 20 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 epoxy resin composition according to 1.   A semiconductor device sealed with the liquid epoxy resin composition according to claim 1.   A flip chip type semiconductor device in which the liquid epoxy resin composition according to claim 1 is injected into a gap between die substrates of a flip chip type semiconductor device, cured and sealed.

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