JP2001207021A - Liquid epoxy resin composition and electronic part device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid epoxy resin composition which exhibits low viscosity and modulus, small warp, and excellent moisture resistance reliability and thermal shock resistance and to provide an electronic part device having an element and/or a bonding area sealed therewith. SOLUTION: This epoxy resin composition essentially comprises (A) an epoxy resin, (B) a curing agent, (C) an alkoxysilyl-terminated polyalkylene oxide compound, (D) a silanol condensation catalyst, (E) a silane coupling agent, and (F) an inorganic filler. The electronic part device has an element and/or a bonding area sealed with the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid epoxy resin composition suitable for encapsulating an electronic component device which requires particularly high reliability, and an element and / or an element sealed with the liquid epoxy resin composition. The present invention relates to an electronic component device having a bonding area.

[0002]

2. Description of the Related Art Conventionally, in the field of device sealing of electronic parts such as transistors and ICs, resin sealing has become the mainstream in terms of productivity and cost, and epoxy resin compositions have been widely used. The reason for this is that the epoxy resin is well balanced in various properties such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products. In addition, in order to reduce the cost, size, thickness, and weight of electronic component devices, and to achieve high performance and high functionality, high-density mounting of elements, finer wiring, multi-layering, multi-pin, The occupation area is increasing.
Along with this, the electronic component devices have become DIP (Dual Inline Pa
ckage), SOGA (Small Outlin) from conventional pin insertion type packages such as PPGA (Plastic Pin Grid Aray).
e J-leaded package), SOP (Small Outline Packag)
e), BGA (Ball Grid Array), CSP (ChipSize P)
The mainstream has been shifted to surface mount packages such as ackage), and bare chip mount packages are also used. As a sealing material used in a surface mount type electronic component device, a liquid epoxy resin composition which is advantageous for a thin and small package from the viewpoint of moldability is often used instead of a conventional solid epoxy resin composition. As a result, the transfer molding method has been replaced by a dispensing method or a printing method.

In a CSP such as a μBGA or a BOC (Board on Chip), only a bonding area for electrically connecting an element and a substrate is sealed, and a sealing material is provided around the element.
Since the center and the like are partially covered, there is a problem that the element and the substrate warp due to the stress generated by the molding shrinkage of the epoxy resin composition and the difference in the coefficient of thermal expansion, thereby significantly reducing the reliability of the package. In addition, in the wafer level CSP that has been recently developed, the wafer is largely warped because one side of a 5 to 8 inch wafer is covered with a sealing material, and there is a problem in carrying, polishing, and dicing operations in the process. There is a problem that device characteristics vary depending on the device. For this reason, the liquid epoxy resin composition used for such applications is required to have a low stress, and as a countermeasure, a method of highly filling an inorganic filler to reduce the thermal expansion coefficient of the sealing material,
Dimeric acid modification to reduce the elastic modulus, flexible epoxy resin such as epoxidized butadiene, cross-linked butadiene,
A method of blending rubber such as acrylic rubber particles, a method of using a resin composition having an ultra-low elastic modulus such as silicone resin, and the like have been proposed.

[Problems to be solved by the invention]

[0004] However, in the technique of highly filling the inorganic filler, there is a limit in reducing the warpage by bringing the thermal expansion coefficient of the sealing material close to the element, and the stress is increased because the elastic modulus of the cured product itself is increased. Insufficient reduction. In the method using a flexible epoxy resin, the elastic modulus of the cured product is reduced, and the warpage can be reduced by stress relaxation. However, the humidity resistance is poor, the viscosity is high, and the workability tends to be poor. In the method of adding rubber, the amount of addition is limited because the viscosity of the liquid epoxy resin composition increases, and a sufficient effect has not been obtained.
In the method using a resin composition having an ultra-low elastic modulus, stress can be remarkably reduced at a low viscosity, and warpage can be reduced.
Since the thermal expansion coefficient is large, defects such as peeling and cutting of the gold wire are liable to occur due to expansion and contraction during a heat cycle, and there is a disadvantage that thermal shock resistance is poor. The present invention has been made in view of such a situation, and has a low viscosity, a low elastic modulus and a small warpage,
An object of the present invention is to provide a liquid epoxy resin composition having excellent moisture resistance reliability and thermal shock resistance, and an electronic component device having an element and / or a bonding area sealed thereby.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a liquid epoxy resin composition has a terminal alkoxysilyl-modified polyalkylene oxide compound, a silanol condensation catalyst and a silane. It has been found that the above object can be achieved by adding a coupling agent, and the present invention has been completed.

That is, the present invention provides (1) (A) an epoxy resin, (B) a curing agent, (C) an alkoxysilyl-modified polyalkylene oxide compound, (D) a silanol condensation catalyst, and (E) a silane coupling agent. And (F) a liquid epoxy resin composition containing an inorganic filler as an essential component,
(2) the liquid epoxy resin composition according to the above (1), wherein the (B) curing agent is at least one of a phenol resin, an aromatic amine, and an acid anhydride; The liquid epoxy resin composition according to the above (2), which is a phenol resin and / or a liquid aromatic amine,
(4) Any one of the above (1) to (3), wherein the (E) silane coupling agent is a silane coupling agent having a functional group that reacts with (A) an epoxy resin and / or (B) a curing agent. (5) The liquid epoxy resin composition according to (4), wherein (E) the silane coupling agent is a silane coupling agent having an NH ₂ CONH— group, and (6) ( C) The compounding amount of the terminal alkoxysilyl-modified polyalkylene oxide compound is (A)
The above (1) to (5), which is 0.4 to 0.95% by weight based on the total amount of the epoxy resin, the (B) curing agent, and the (C).
And (7) an electronic device having an element and / or a bonding area sealed with the liquid epoxy resin composition according to any one of (1) to (6). Related to component devices.

[0007]

DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The epoxy resin is not particularly limited, and an epoxy resin generally used in a liquid epoxy resin composition can be used.If the composition is in a liquid state, either a solid or a liquid may be used in combination. May be. For example, phenols and aldehydes such as glycidyl ether epoxy resins and orthocresol novolac epoxy resins obtained by the reaction of epichlorohydrin with bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalene diol, hydrogenated bisphenol A, etc. Epoxidized novolak resin obtained by condensation or co-condensation with phthalic acid, glycidyl ester type epoxy resin obtained by reaction of polychlorinated acid such as dimer acid and epichlorohydrin, diaminodiphenylmethane, polyamine such as isocyanuric acid and Glycidylamine type epoxy resin obtained by reaction of epichlorohydrin, linear aliphatic epoxy resin obtained by oxidizing olefin bond with peracid such as peracetic acid, and alicyclic epoxy resin And the like resins may be used in combination of two or more even with these alone. It is preferable that these epoxy resins are sufficiently purified and have few ionic impurities. For example, the amount of free Na ions and free Cl ions is preferably 500 ppm or less.

The curing agent (B) used in the present invention is not particularly limited, and those generally used as curing agents for epoxy resins can be used. Examples of the curing agent include phenol resins, aromatic amines and acid anhydrides. Is preferred,
A phenol resin is more preferable from the viewpoint of storage stability, and an aromatic amine is more preferable from the viewpoint of adhesiveness.
If the composition is liquid, either one of a solid curing agent and a liquid curing agent may be used, or both may be used in combination. The phenolic resin is not particularly limited as long as it has one or more phenolic hydroxyl groups in the molecule.
Phenols such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and / or α-
Naphthol, β-naphthol, a novolak-type phenol resin obtained by condensing or co-condensing a naphthol such as dihydroxynaphthalene and a compound having an aldehyde group such as formaldehyde under an acidic catalyst, allylated bisphenol A, allylated bisphenol F, Phenol aralkyl resin synthesized from phenols such as allylated naphthalene diol, phenol novolak, phenol and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl, naphthol
And aralkyl resins. These may be used alone or in combination of two or more. Among them, a liquid phenol resin is preferable. The aromatic amine is not particularly limited as long as it is an amine compound having an aromatic ring. For example, commercially available products such as EpiCure W, EpiCure Z (trade name of Yuka Shell Epoxy Co., Ltd.), Kayahard A-
A, Kayahard AB, Kayahard AS (trade name, manufactured by Nippon Kayaku Co., Ltd.), Thothamine HM-205 (trade name, manufactured by Toto Kasei Co., Ltd.), Adeka Hardner EH-101
(Trade name of Asahi Denka Kogyo KK), Epomic Q-64
0, Epomic Q-643 (trade name, manufactured by Mitsui Chemicals, Inc.), DETDA80 (trade name, manufactured by Lonza) and the like may be used, and these may be used alone or in combination of two or more. Above all, a liquid aromatic amine is preferable from the viewpoint of viscosity, and 3,3 ′ is preferable from the viewpoint of storage stability.
More preferred is a liquid aromatic amine containing -diethyl-4,4'-diaminodiphenylmethane and / or diethyltoluenediamine as a main component. The acid anhydride is not particularly limited, for example, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, hymic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. These may be used alone or in combination of two or more.

The equivalent ratio of the epoxy resin (A) to the curing agent (B) is not particularly limited.
It is preferable to set the range of 1.6 equivalents,
1.4 equivalents are more preferred, and 0.8-1.2 equivalents are even more preferred. 0.6. When the amount is out of the range of from 1.6 to 1.6 equivalents, the curing reaction tends to be insufficient and the reliability tends to decrease. Here, the equivalent of the phenolic resin is calculated assuming that one epoxy group reacts with one phenolic hydroxyl group, and the equivalent of the aromatic amine is one in which one active hydrogen of the amino group reacts with one epoxy group. Is calculated as
The equivalent of acid anhydride is calculated as one acid anhydride group reacts with one epoxy group.

The (C) terminal alkoxysilyl-modified polyalkylene oxide compound used in the present invention is a compound having a structure in which a linear polyalkylene oxide is a main skeleton and an alkoxysilyl group is added to a terminal. Examples of the polyalkylene oxide of the main skeleton include a homopolymer, a random polymer, and a block copolymer obtained by ring-opening polymerization of one or more alkylene oxides.
They may be used alone or in combination of two or more.
As a commercially available product, Cyril (trade name, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) can be mentioned. The alkoxysilyl group may be added to only one terminal of the compound having polyalkylene oxide as a main skeleton, but is preferably added to both terminals. When a compound added to only one terminal is used, the crosslinking at the time of curing becomes insufficient and the physical properties of the cured product tend to be reduced.
The alkoxysilyl group added to the terminal is represented by the following general formula (I).

## STR1 ## _{^{-Si (R 1) n (OR}} 2) 3-n ...... (I) where integer n in the formula 0 to 2, R ^1, R ² represents an alkyl group, in the same It may be different. Among them,
R ¹ and R ² are preferably an alkyl group having 1 to 5 carbon atoms. Further, n is preferably 1. When n = 0, the storage stability of the resin composition tends to decrease, and n = 2
In such a case, the crosslinking at the time of curing becomes insufficient and the physical properties of the cured product tend to decrease.

In order to achieve the effect of the present invention, the compounding amount of (C) the alkoxysilyl-terminated polyalkylene oxide compound is 0.4 to 0.4% based on the total amount of (A), (B) and (C). It is preferably set to 0.95% by weight, more preferably 0.5 to 0.8% by weight, and 0.6 to 0.8% by weight.
0.75% by weight is more preferred. The weight average molecular weight of the (C) terminal alkoxysilyl-modified polyalkylene oxide compound is not particularly limited, but is preferably from 1,000 to 10,000, more preferably from 2,000 to 5,000. If the weight average molecular weight is less than 1,000, the cured product tends to be brittle, and if it exceeds 10,000, the viscosity tends to be too high.

The silanol condensation catalyst (D) used in the present invention must be blended as a concomitant component of the (C) alkoxysilyl-modified polyalkylene oxide compound (C), and is not particularly limited. .
For example, tin stearate, metal carboxylate such as lead octylate, di-n-butyltin dilaurate, organic tin compounds such as dioctyltin dilaurate, aluminum alcoholate, aluminum chelate compound, titanium chelate compound and the like. May be used alone or in combination of two or more. The compounding amount of the (D) silanol condensation catalyst is 0.1 to 5 parts by weight based on 100 parts by weight of the (C) terminal alkoxysilyl-modified polyalkylene oxide compound.
It is preferably set to be parts by weight, 0.3
-2 parts by weight is more preferable, and 0.5-1 part by weight is further preferable.

The (E) silane coupling agent used in the present invention includes a crosslinking agent for the inorganic filler and the resin, and (C) an alkoxysilyl-modified polyalkylene oxide compound with (A) an epoxy resin and / or (B) Used as a crosslinking agent for the curing agent. Therefore, the silane coupling agent (E) is not particularly limited, and a silane coupling agent generally used in a liquid epoxy resin composition can be used.
It is preferable to use a silane coupling agent having a functional group that reacts with (A) the epoxy resin and / or (B) the curing agent. For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aniline Examples thereof include linopropyltrimethoxysilane, γ-ureidotrimethoxysilane, γ-dibutylaminopropyltrimethoxysilane, and hydroxypropyltrimethoxysilane. These may be used alone or in combination of two or more. Among them, those having a nitrogen atom such as aminosilane are preferable from the viewpoint of reactivity with the epoxy resin and adhesiveness with various base materials,
From the viewpoint of storage stability, ureidosilanes such as alkoxysilanes having an NH ₂ CONH— group are more preferable.
The compounding amount of (E) the silane coupling agent is (C) the terminal alkoxysilyl-modified polyalkylene oxide compound 10
It is preferably set to be 0.5 to 10 parts by weight relative to 0 parts by weight, more preferably 1 to 7 parts by weight,
2-5 parts by weight are more preferred.

The inorganic filler (F) used in the present invention includes, for example, silica such as fused silica and crystalline silica, alumina such as calcium carbonate, clay and alumina oxide, silicon nitride, silicon carbide, boron nitride and calcium silicate. , Potassium titanate, aluminum nitride, beryllia, zirconia, zircon, powders of fosterite, steatite, spinel, mullite, titania, etc., or spherical beads or glass fibers thereof. further,
Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate and the like. These inorganic fillers may be used alone or in combination of two or more. Among them, silica is preferred, and spherical silica is more preferred from the viewpoint of fluidity and permeability into the fine gaps of the liquid sealing material. (F) The average particle size of the inorganic filler is 1 to 20 μm, particularly in the case of spherical silica.
m is preferable, and a range of 2 to 10 μm is more preferable. If the average particle size is less than 1 μm, the liquid epoxy resin composition tends to be poor in dispersibility and the liquid epoxy resin composition tends to be imparted with thixotropic properties and the flowability tends to be inferior, and if it exceeds 20 μm, the filler tends to precipitate. In addition, the permeability and fluidity of the liquid epoxy resin composition into the fine gaps tend to decrease, which tends to cause voids and unfilling. (F)
The amount of the inorganic filler is 20% of the liquid epoxy resin composition.
To 90% by weight, more preferably 30 to 85% by weight, even more preferably 55 to 85% by weight.
80% by weight. If the amount is less than 20% by weight, the effect of reducing the thermal expansion coefficient is low and the thermal shock resistance tends to be inferior. If the amount is more than 90% by weight, the viscosity of the liquid epoxy resin composition increases, and the fluidity, permeability and dispensing are increased. Tends to cause a decrease in the performance.

An organic solvent can be added to the liquid epoxy resin composition of the present invention as needed to reduce the viscosity. In particular, when a solid epoxy resin and a curing agent are used, it is necessary to incorporate an organic solvent in order to obtain a liquid composition. The organic solvent is not particularly limited, but preferably has a boiling point of 100 ° C. or higher from the viewpoint of avoiding the formation of bubbles due to rapid volatilization during heat curing. For example, toluene, xylene, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, 2- (2
-Butoxyethoxy) ethanol, dipropylene glycol methyl ether, 4-hydroxy-4-methyl-2
-Pentanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, γ-
Butyrolactone, etc., and these may be used alone or in combination of two or more.

The liquid epoxy resin composition of the present invention comprises a cycloamidine compound, a tertiary amine, an imidazole,
Commonly used curing accelerators such as organic phosphines, phosphorus compounds, tetraphenylboron salts and derivatives thereof can be used alone or in combination of two or more as required. In particular, when a phenol resin and / or an acid anhydride is used as a curing agent, it is preferable to add a curing accelerator. The amount of the curing accelerator is
The amount is not particularly limited as long as the curing acceleration effect is achieved, but is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the (A) epoxy resin and (B) the curing agent. The amount is more preferably 0.5 to 5 parts by weight, and still more preferably 1 to 3 parts by weight. If the amount is less than 0.1 part by weight, the curability in a short time tends to be inferior. If the amount exceeds 10 parts by weight, the curing speed tends to be too fast to obtain a good cured product.

Further, the liquid epoxy resin composition of the present invention may further comprise, as other additives, red phosphorus, phosphate ester,
Melamine, melamine derivatives, compounds having a triazine ring, nitrogen-containing compounds such as cyanuric acid derivatives, isocyanuric acid derivatives, phosphorus-nitrogen-containing compounds such as cyclophosphazene, metal compounds such as zinc oxide, iron oxide, molybdenum oxide, ferrocene, and trioxide Antimony, antimony tetroxide,
Antimony oxides such as antimony pentoxide, conventionally known flame retardants such as brominated epoxy resins, hydrotalcites, magnesium, aluminum, titanium, zirconium, conventionally known ion trapping agents such as hydrated oxides of elements such as bismuth, Release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, polyethylene oxide, etc., stress relievers such as silicone oil and silicone rubber powder, dyes, coloring agents such as carbon black, diluents, A leveling agent, an antifoaming agent and the like can be added as required.

The liquid epoxy resin composition of the present invention can be prepared by any method as long as the above-mentioned various components can be uniformly dispersed and mixed. As a general method, a predetermined amount of the components is weighed. Then, a method of carrying out dispersion kneading with a three-roll mill, a mill or the like can be used.

The electronic component device obtained by sealing the element and / or the bonding area with the liquid epoxy resin composition obtained by the present invention includes a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer and the like. Active elements such as semiconductor chips, transistors, diodes, thyristors, capacitors, resistors,
An electronic component device obtained by mounting an element such as a resistance element, a coil, or a passive element such as a switch, and sealing a necessary portion with the liquid epoxy resin composition of the present invention is exemplified.
As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, and a terminal portion of an element such as a bonding pad and a lead portion are connected by wire bonding or a bump, and then the liquid epoxy resin composition of the present invention is used. PLCC sealed by dispensing method etc.
(Plastic Leaded Chip Carrier), QFP (Quad Flat)
Package), SOP (Small Outline Package), SO
J (Small Outline J-leaded package), TSOP (Th
in Small Outline Package), TQFP (Thin Quad Fl)
at package) and a semiconductor chip connected to a tape carrier via bumps, and a TCP (Tape Carrier P) sealed with a liquid epoxy resin composition of the present invention.
active elements such as semiconductor chips, transistors, diodes, thyristors, etc., and / or passive elements such as capacitors, resistors, coils, etc., connected to wiring formed on a wiring board or glass by wire bonding, flip chip bonding, soldering, etc. The element is mounted on an organic substrate on which a terminal for connecting a COB (Chip On Board) module, a hybrid IC, a multi-chip module, and a wiring board is formed by sealing the element with the liquid epoxy resin composition of the present invention, and a bump or a wire is provided. After connecting the element and the wiring formed on the organic substrate by bonding, a BGA (Ball Grid Array) and a CSP (Chip Size Pac) in which the element and / or the bonding area are sealed with the liquid epoxy resin composition of the present invention.
kage). Further, the liquid epoxy resin composition of the present invention can be effectively used for printed circuit boards.

Examples of a method for sealing a device and / or a bonding area using the liquid epoxy resin composition of the present invention include a dispensing method, a casting method, and a printing method.

[0021]

Next, the present invention will be described with reference to examples, but the scope of the present invention is not limited to these examples.

Examples 1 to 5 and Comparative Examples 1 to 9 Bisphenol A type epoxy resin (Epicoat 82 manufactured by Yuka Shell Epoxy Co., Ltd.) was used as the epoxy resin.
8), dimer acid-modified epoxy resin (trade name: Epicoat 878, manufactured by Yuka Shell Epoxy Co., Ltd.), epoxy-terminated butadiene (trade name: EPB-1, manufactured by Nippon Soda Co., Ltd.)
3), a phenol resin as a curing agent (trade name MEH-8000 manufactured by Meiwa Kasei Co., Ltd.), an aromatic amine (trade name Kayahard A-A manufactured by Nippon Kayaku Co., Ltd.), an acid anhydride (trade name manufactured by Hitachi Chemical Co., Ltd.) MHAC-HR), Silyl SAT010 (trade name, manufactured by Kaneka Chemical Industry Co., Ltd.) as a terminal alkoxysilyl-modified polyalkylene oxide compound, dibutyltin silaurate (Wako Pure Chemical Industries, Ltd.) as a silanol condensation catalyst, silane coupling agent As ureidosilane (trade name AY43-031 manufactured by Dow Corning Silicone Toray Co., Ltd.) or aminosilane (trade name SH6020 manufactured by Dow Corning Toray Silicone Co., Ltd.) and SE-8 (trade name by Tokuyama Corporation) as an inorganic filler ), 2-undecylimidazole as a curing accelerator ( A cross-linked acrylic rubber (trade name: Staphyloid AC-3355, manufactured by Takeda Pharmaceutical Co., Ltd.) was compounded with the composition shown in Table 1, respectively, as a three-roll mill. After kneading and dispersing in, vacuum degassing was performed to produce liquid epoxy resin compositions of Examples and Comparative Examples.

[0023]

[Table 1]

The liquid epoxy resin compositions of Examples and Comparative Examples were evaluated by the following tests. The package and the test piece were prepared by heating the liquid epoxy resin composition at 150 ° C.
It was formed by molding by a dispense method under a heating condition of 3 hours. Table 2 shows the evaluation results. (1) Viscosity and storage stability The viscosity (Pa · s) at 25 ° C. was measured using an E-type viscometer (Tokyo Keiki Co., Ltd.). The storage stability was evaluated by measuring the time-dependent change in viscosity of the liquid epoxy resin composition left at 25 ° C., and evaluating the number of days when the viscosity became twice the initial value.
(2) Modulus of elasticity The liquid epoxy resin composition was formed into a sheet having a thickness of 0.4 mm, and the sheet was cut into a strip having a size of 5 mm x 30 mm to obtain a test piece, and a dynamic viscoelasticity measuring device DVE type (manufactured by Rheology Co., Ltd.) ), At a heating rate of 3 ° C./min, a measurement temperature of −120 to 250 ° C., and a frequency of 10 Hz.
The elastic modulus (GPa) at 25 ° C. was read. (3) Warp The liquid epoxy resin composition was placed on a silicon chip (25 mm ×
A test piece molded to a thickness of 0.2 mm on a 25 mm × 200 μm thick) was traced diagonally on the chip back surface using a surface roughness meter (manufactured by Kosaka Laboratory Co., Ltd.) to determine the amount of warpage (μm). (4) Moisture resistance Adhesive strength A test piece molded on one side of a 30 μm-thick aluminum foil or 75 μm-thick polyimide film was subjected to Autograph AGS.
Using a -500A type (manufactured by Shimadzu Corporation), at a head speed of 30 mm / min, an aluminum foil or polyimide film having a width of 10 mm is peeled off in the vertical direction, and its strength (peel strength: N / m) is reduced. It was measured. This measurement was performed immediately after molding the test piece, and at 121 ° C., 2 atm, 100
Performed after 168 h of treatment under PCT conditions of% RH. (5) Moisture resistance reliability The BGA package for evaluation (chip: TEG forming an aluminum zigzag wiring) sealed at the above molding conditions is 121 ° C., 2a.
After 240 hours of treatment under the PCT condition of tm and 100% RH, the presence or absence of peeling of the liquid epoxy resin composition from the chip and the polyimide film was observed using an ultrasonic flaw detector AT5500 (manufactured by Hitachi Construction Machinery Co., Ltd.). Further, disconnection and corrosion failure of the aluminum wiring and pad were confirmed by a conduction test and an infrared microscope, and evaluated by the number of defective packages / the number of measurement packages. (6) Thermal shock resistance The same BGA package for evaluation as in the above (5) was replaced with -50
1000 cycles of heat treatment at 30 ° C./150° C. for 30 minutes each, a conduction test was conducted to check for disconnection failure of the aluminum wiring, and the evaluation was made by the number of defective packages / the number of measurement packages.

[0025]

[Table 2]

In Comparative Example 1 of the present invention containing no (F) inorganic filler, the thermal shock resistance was remarkably poor, and Comparative Example 2 not containing (C) an alkoxysilyl-modified polyalkylene oxide compound and (D) a silanol condensation catalyst. In this case, warpage and thermal shock resistance are remarkably inferior. In Comparative Examples 3 to 6, which are conventional methods for improving warpage, Comparative Examples 3 and 4 in which a flexible epoxy resin was blended did not sufficiently improve the warpage and were inferior in moisture resistance reliability. Excellent reliability, but high viscosity and poor thermal shock resistance. Further, even in Comparative Example 6 in which the inorganic filler was highly loaded, the warpage improvement was not sufficient,
High elastic modulus, inferior in moisture resistance reliability and thermal shock resistance.
(B) In Comparative Example 7 containing no curing agent, the curability was extremely reduced and molding was not possible, and in Comparative Example 8 in which a curing accelerator was added in place of the curing agent, the moisture resistance adhesion and moisture resistance reliability were poor.
(E) In Comparative Example 9 containing no silane coupling agent,
Poor in moisture resistance adhesive strength, humidity resistance reliability and thermal shock resistance. In contrast, all of Examples 1 to 5 of the present invention have a low viscosity, a low elastic modulus, a small warpage, a high adhesive strength even after a high-temperature and high-humidity treatment, and have excellent moisture resistance reliability and thermal shock resistance. In particular, Examples 1 and 2 using a phenolic resin curing agent and a ureidosilane coupling agent are excellent in storage stability, Example 3 using an aromatic amine-based curing agent, and Example 5 using an aminosilane coupling agent. Is remarkably excellent in moisture resistance.

[0027]

The liquid epoxy resin composition according to the present invention has a low viscosity, a low elastic modulus, a small warpage, and a high adhesive strength even after high-temperature and high-humidity treatment, as shown in the examples. If the element is sealed with an object, an electronic component device with excellent moisture resistance reliability and thermal shock resistance can be obtained, so that it can be used for packaging at the time of shipping and for controlling moisture absorption in the manufacturing process of electronic component devices such as semiconductor devices. And its industrial value is great.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 10, 2001 (2001.5.1
0)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 6

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

That is, the present invention provides (1) (A) an epoxy resin, (B) a curing agent, (C) an alkoxysilyl-modified polyalkylene oxide compound, (D) a silanol condensation catalyst, and (E) a silane coupling agent. And (F) a liquid epoxy resin composition containing an inorganic filler as an essential component,
(2) the liquid epoxy resin composition according to the above (1), wherein the (B) curing agent is at least one of a phenol resin, an aromatic amine, and an acid anhydride; The liquid epoxy resin composition according to the above (2), which is a phenol resin and / or a liquid aromatic amine,
(4) Any one of the above (1) to (3), wherein the (E) silane coupling agent is a silane coupling agent having a functional group that reacts with (A) an epoxy resin and / or (B) a curing agent. (5) The liquid epoxy resin composition according to (4), wherein the (E) silane coupling agent is a silane coupling agent having an NH ₂ CONH— group, and (6) ( C) The compounding amount of the terminal alkoxysilyl-modified polyalkylene oxide compound is (A)
The above (1), which is 0.4 to 0.95 parts by weight based on 1 part by weight of the total amount of the epoxy resin, the (B) curing agent, and the (C).
The liquid epoxy resin composition according to any one of (1) to (5),
And (7) an electronic component device including an element and / or a bonding area sealed with the liquid epoxy resin composition according to any one of (1) to (6).

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

In order to achieve the effects of the present invention, the compounding amount of (C) the alkoxysilyl-terminated polyalkylene oxide compound is 0 to 1 part by weight of the total amount of (A), (B) and (C). It is preferably set to 0.4 to 0.95 parts by weight, more preferably 0.5 to 0.8 parts by weight, and more preferably 0.5 to 0.8 parts by weight.
6 to 0.75 parts by weight is more preferred. The weight average molecular weight of the (C) terminal alkoxysilyl-modified polyalkylene oxide compound is not particularly limited, but may be from 1,000 to 1,000.
0 is preferable, and 2000 to 5000 is more preferable. If the weight average molecular weight is less than 1,000, the cured product tends to be brittle, and if it exceeds 10,000, the viscosity tends to be too high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 23/31 F term (Reference) 4J002 CC032 CC042 CC052 CC072 CD011 CD041 CD051 CD061 CD101 CD111 CD131 CD141 CE002 CH053 CP183 DE099 DE139 DE189 DE239 DF019 DJ009 DJ019 EC077 EG047 EL136 EL146 EN056 EX038 EX068 EX078 EZ007 EZ047 FD019 FD142 FD146 FD153 FD157 FD158 4J036 AA01 AB07 AD08 AD20 AF06 AF07 AG07 AH07 AJ18 DB15 DB18 FB13 DB02 DB13 FB02

Claims (7)

[Claims] (1) an epoxy resin, (B) a curing agent,
A liquid epoxy resin composition comprising (C) an alkoxysilyl-modified polyalkylene oxide compound, (D) a silanol condensation catalyst, (E) a silane coupling agent, and (F) an inorganic filler as essential components. 2. The liquid epoxy resin composition according to claim 1, wherein (B) the curing agent is at least one of a phenol resin, an aromatic amine, and an acid anhydride. 3. The liquid epoxy resin composition according to claim 2, wherein (B) the curing agent is a liquid phenol resin and / or a liquid aromatic amine. 4. The silane coupling agent according to claim 1, wherein (E) the silane coupling agent is a silane coupling agent having a functional group that reacts with (A) an epoxy resin and / or (B) a curing agent. Liquid epoxy resin composition. 5. The method according to claim 1, wherein (E) the silane coupling agent is NH ₂ C
The liquid epoxy resin composition according to claim 4, which is a silane coupling agent having an ONH- group. 6. The compounding amount of (C) the alkoxysilyl-modified polyalkylene oxide compound is 0.4% based on the total amount of (A) epoxy resin, (B) curing agent and (C).
The liquid epoxy resin composition according to any one of claims 1 to 5, wherein the content is from 0.95 to 0.95% by weight. 7. An electronic component device comprising an element and / or a bonding area sealed with the liquid epoxy resin composition according to claim 1.