JP2000017052A - Epoxy resin composition and electric parts device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin compsn. to give a semiconductor device being free from the occurrence of voids and having excellent curability, adhesiveness to a passivation membrane and moisture resistance on moisture absorption. SOLUTION: This compsn. contains as the essential components (A) an epoxy resin having two or more epoxy groups in the mol., (B) a phenol resin having two or more phenolic groups in the mol., and (C) a curing accelerator expressed by the formula (wherein R1 and R2 are each hydrogen, a 1-6C alkyl group, or a 1-6C alkoxyl group, and may be or different same except a case when the both are hydrogen, R3 is hydrogen or a 1-6C alkyl group; and (m) is 1 or 2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition suitable as a molding material, a laminate or an adhesive material, and an electronic component device obtained by sealing an element with the composition.

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been widely used as materials for molding materials, laminates and adhesives, and epoxy resin compositions have been widely used in the field of device sealing of electronic parts such as transistors and ICs. Have been. The reason for this is that the epoxy resin is balanced in various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness to insert products. In particular, the combination of an ortho-cresol novolak type epoxy resin and a phenol novolak curing agent is excellent in these balances.
It has become mainstream as a base resin for molding materials for C sealing. Further, amine compounds such as tertiary amine and imidazole, and phosphorus compounds such as phosphines and phosphonium are generally used as the curing accelerator.

[0003]

In recent years, electronic components have been increasingly mounted on printed wiring boards at a high density. With this trend, electronic components have become more prevalent than conventional pin insertion type packages but surface mount type packages. It is becoming. IC, LSI
In such surface mount ICs, the occupied volume of the device in the package has been gradually increased in order to increase the packaging density, and the thickness of the package has become extremely thin. In addition, pin-insertion type packages are not exposed to high temperatures because the pins are inserted into the wiring board and then soldered from the back side of the wiring board. After the temporary fixing, the solder is processed by a solder bath or a reflow device, so that it is directly exposed to the soldering temperature. As a result, when the IC package absorbs moisture, the moisture absorbed rapidly expands during soldering, leading to a package crack, which is a major problem.

In recent years, a resin composition containing a large amount of an inorganic filler has been proposed in order to improve the package crack resistance during reflow, that is, the so-called reflow crack resistance. However, an increase in the amount of the inorganic filler causes a decrease in fluidity during molding, and impairs the molding such as defective filling and voids, and the like.
Since the bonding wire of the C chip is broken and conduction failure occurs, the performance of the molded product is deteriorated, so that the compounding amount of the inorganic filler is limited. As a result, remarkable improvement in reflow crack resistance cannot be expected. In particular, when a phosphorus-based curing accelerator such as triphenylphosphine or an amine-based curing accelerator such as 1,8-diazabicyclo [5.4.0] undecene-7 is used, fluidity is low and reflow crack resistance is remarkably improved. The fact is that you cannot expect. Furthermore, when a phosphine-based curing accelerator is used, there is a problem that a large amount of voids are generated depending on the type of epoxy resin / curing agent used.

As a method for solving these problems, Japanese Patent Application Laid-Open No. Hei 7-228672 discloses a method of accelerating the addition of a phosphine having three phenyl groups having an electron donating substituent with maleic anhydride or quinones. Although a method of using as an agent is disclosed, there is a problem in that the adhesion to a passivation film formed on a semiconductor chip is low, and the moisture resistance reliability is deteriorated due to peeling.

The present invention has been made in view of such circumstances, and an epoxy resin composition which is free from voids, has excellent curability at the time of moisture absorption, excellent adhesion to a passivation film, and excellent moisture resistance, and a composition thereof. It is intended to provide an electronic component device provided with an element sealed with a.

[Means for Solving the Problems]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that by adding an addition reaction product of a specific triphenylphosphine and a quinone compound, no void is generated, and An epoxy resin composition with excellent curability and excellent adhesion to the passivation film was found,
The present invention has been completed.

Specifically, the present invention provides (1) (A) an epoxy resin having two or more epoxy groups in one molecule,
(B) a phenolic resin having two or more phenolic hydroxyl groups in one molecule, (C) a curing accelerator represented by the following formula (I),

Embedded image (Here, R ¹ and R ² are selected from hydrogen, an alkyl group having 1 to 6 carbon atoms and an alkoxyl group having 1 to 6 carbon atoms, and may be the same or different except when both are hydrogen. R
³ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and m represents 1 or 2. (2) an epoxy resin composition characterized in that it contains 55% by volume or more of an inorganic filler (D) based on the whole composition. Epoxy resin composition,
(3) The equivalent ratio of the epoxy group of the epoxy resin (A) to the phenolic hydroxyl group of the phenol resin (B) ((B) /
(A)) is 0.5 to 2, the epoxy resin composition according to the above (1) or (2), (4)
The epoxy resin composition according to any one of the above (1) to (3), wherein the component (A) contains an epoxy resin of the following formula (II) and / or (III):

Embedded image (Here, each of the four R ⁴ and R ⁵ in the formula may be the same or different, and represents hydrogen or a methyl group.) (5)
(B) The component according to any one of the above (1) to (4), wherein the component contains at least one of the phenolic resins represented by the following formulas (IV), (V) and (VI). Epoxy resin composition,

Embedded image (Here, X, Y, and Z represent 0 to 10.) (6) An electronic component device including an element sealed with the epoxy resin composition according to any one of (1) to (5). is there.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The epoxy resin (A) used in the epoxy resin composition of the present invention is commonly used and is not particularly limited. Examples thereof include bisphenol A, bisphenol F, resorcinol, and phenol. Glycidyl ethers of phenols such as novolak and cresol novolak, glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol, glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid, aniline and isocyanuryl Glycidyl-type or methylglycidyl-type epoxy resins such as those obtained by replacing active hydrogen bonded to a nitrogen atom such as an acid with a glycidyl group, and vinylcyclohexene diepoxy obtained by epoxidizing an olefin bond in a molecule. Sid, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2- (3,4-epoxy) cyclohexyl -
5,5-spiro (3,4-epoxy) cyclohexane-
Alicyclic epoxy resin such as m-dioxane, glycidyl ether of para-xylylene-modified phenol resin, glycidyl ether of meta-xylylene / para-xylylene-modified phenol resin, glycidyl ether of terpene-modified phenol resin, glycidyl ether of dicyclopentadiene-modified phenol resin, cyclopentadiene-modified Glycidyl ether of phenolic resin, glycidyl ether of polycyclic aromatic ring-modified phenolic resin, glycidyl ether of phenolic resin containing naphthalene ring, biphenyl type epoxy resin, halogenated phenol novolak type epoxy resin, etc., alone or in combination of two or more Can be used. Among these epoxy resins, those represented by the following general formulas (II) and (III) are preferable in terms of fluidity and reflow resistance, and among them, from the viewpoint of reflow resistance, 4,4′-bis ( 2,3-epoxypropoxy)
-3,3 ', 5,5'-Tetramethylbiphenyl is more preferable, and 4,4'-bis (2,3-epoxypropoxy) biphenyl is more preferable from the viewpoint of moldability and heat resistance. These epoxy resins of the formulas (II) and (III) may be used alone or in combination. However, in order to exhibit the performance, the total amount of the epoxy resin of the component (A) is required. It is preferable to use 60% by weight or more.

[0010]

Embedded image (Here, each of the four R ⁴ and R ⁵ in the formula may be the same or different and represents hydrogen or a methyl group.)

The phenolic resin having two or more phenolic hydroxyl groups in one molecule of the component (B) used in the epoxy resin composition of the present invention is not particularly limited, and known phenolic resins can be widely used. For example, phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde;
Resins obtained by condensing or co-condensing aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst, para-xylylene-modified phenol resin, meta-xylylene / para-xylylene-modified phenol resin, melamine-modified phenol resin, and terpene-modified phenol resin And a dicyclopentadiene-modified phenol resin, a cyclopentadiene-modified phenol resin, a polycyclic aromatic ring-modified phenol resin, and the like, and these can be used alone or in combination of two or more. These phenolic resins can be used without limitation in molecular weight, softening point, hydroxyl equivalent, and the like. Among them,
From the viewpoint of curability, those represented by the following formulas (IV), (V), and (VI) are preferable, and the structure represented by formula (V) is more preferable from the viewpoint of low moisture absorption. These formulas (IV), (V),
The phenolic resin of the formula (VI) may be used alone or in combination of any two or all three types. It is preferable to use a total of 60% by weight or more.

[0012]

Embedded image X, Y and Z in the above formulas (IV), (V) and (VI) are 0
The numbers from 10 to 10 are shown. If each exceeds 10, the melt viscosity of the component (B) will increase, so that the viscosity of the epoxy resin composition during melt molding will also increase, resulting in poor filling and bonding wires (gold wires connecting the element and the lead). Easily cause deformation. Therefore, X, Y and Z are 0
It is necessary to be in the range of 10 to 10, but it is more preferable to set the average in the range of 1 to 4 in one molecule.

In the present invention, the mixing ratio of the epoxy resin (A) to the phenol compound (B) is such that the ratio of the hydroxyl equivalent of the phenol resin to the epoxy equivalent of the epoxy resin is in the range of 0.5 to 2.0. It is preferably set to 0.7, more preferably 0.7 to 1.5, and still more preferably 0.8 to 1.3. If it is less than 0.5, the curing of the epoxy resin is insufficient, and the heat resistance, moisture resistance and electric properties of the cured product are likely to be inferior. On the other hand, if it exceeds 1.5, the phenolic resin component becomes excessive and a large amount of phenolic hydroxyl groups remain in the cured resin, so that the electrical properties and moisture resistance tend to deteriorate.

The curing accelerator of the component (C) used in the epoxy resin composition of the present invention is not particularly limited as long as the following formula (I) is satisfied.

Embedded image R ¹ and R ² in the above formula (I) represent hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl,
It is selected from an alkyl group having 1 to 6 carbon atoms such as an isopropyl group and a t-butyl group, and an alkoxyl group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group. May be the same or different except when both are hydrogen. R ³ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and m represents 1 or 2
Is shown. Examples of such a compound include the compounds shown in Table 1, and these may be used alone or in combination of two or more. Among these, an exemplary compound in which R ³ is H is preferable in terms of curability, an exemplary compound in which R ² is H and m is 1 is preferable in terms of PIQ peel adhesion,
Exemplary compounds in which ¹ is a methyl group are preferable because they exhibit good moisture-curing properties. Although these exemplified compounds are not particularly limited in the production method, they can be obtained by a method in which an organic phosphine and quinone are subjected to an addition reaction in an organic solvent and isolated. Further, after an organic phosphine and a quinone are subjected to an addition reaction in the phenol resin of the component (B), the phosphine can be used as it is, without being isolated, dissolved in the phenol resin.

[0015]

[Table 1]

The resin composition of the present invention may contain, in addition to the component (C), at least one compound generally used as a curing accelerator for accelerating the curing reaction between an epoxy resin and a compound having a phenolic hydroxyl group. can do. Examples of these curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5 and 1,8-diazabicyclo [5.4.0] undecene-7 or derivatives thereof. Phenol novolak salts of diazabicycloalkenes and derivatives thereof, such as 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl ) Tertiary amines such as phenol, 2
-Methylimidazole, 2-phenylimidazole, 2
Imidazoles such as -phenyl-4-methylimidazole and 2-heptadecylimidazole; tetra-substituted phosphonium-tetra-substituted borates such as tetraphenylphosphonium-tetraphenylborate; 2-ethyl-4-methylimidazole-tetraphenylborate; N- Tetraphenylboron salts such as methylmorpholine / tetraphenylborate, triphenylphosphine, betaine-type addition products of triphenylphosphine and p-benzoquinone, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) ) Phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine,
Organic phosphines such as tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, or complexes of these organic phosphines with organic borons. No.

When these curing accelerators are used in combination,
The compounding amount of the component (C) is preferably at least 30% by weight, more preferably at least 50% by weight, based on the total amount of the curing accelerator. When the amount of the component (C) is less than 30% by weight, voids are generated, the hardness at the time of moisture absorption is reduced, the adhesion to the passivation film is reduced, and the effects of the present invention are reduced. The total blending amount of all the curing accelerators including the component (C) is not particularly limited as long as the amount can reduce the voids, improve the curability during moisture absorption, improve the adhesion to the passivation film, and improve the fluidity. However, the amount is preferably 0.1 to 10 parts by weight, more preferably 1 to 7.0 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin (A) and the phenol resin (B). It is. If the amount is less than 0.1 part by weight, it is difficult to cure in a short time, and if it exceeds 10 parts by weight, the curing speed is too fast to obtain a good molded product.

The inorganic filler (D) to be blended in the resin composition of the present invention is not particularly limited. Examples thereof include fused silica, crystalline silica, glass, alumina, calcium carbonate,
Fine powder of zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, mica, etc. Beads and the like. Further, as the inorganic filler having a flame retardant effect, aluminum hydroxide, magnesium hydroxide, zinc borate, and the like,
These may be used alone or in combination. Among the above-mentioned inorganic fillers, fused silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity.

The amount of the inorganic filler (D) is preferably in the range of 55 to 90% by volume based on the whole resin composition. These inorganic fillers are added for the purpose of improving the thermal expansion coefficient, thermal conductivity, elastic modulus, etc. of the cured product. If the amount is less than 55% by volume, these properties cannot be sufficiently improved. %, The viscosity of the resin composition significantly increases, the fluidity decreases, and molding tends to be difficult. The average particle size of the inorganic filler (D) is 1 to 50 μm.
m is preferable, and 10 to 30 μm is more preferable.
If it is less than 1 μm, the viscosity of the resin composition tends to increase, and
When the average particle size exceeds μm, the resin component and the filler tend to separate from each other, and the cured product tends to be non-uniform, the characteristics of the cured product vary, and the filling property into narrow gaps tends to decrease. From the viewpoint of fluidity, the inorganic filler of the component (D) preferably has a spherical shape rather than a square shape, and preferably has a wide particle size distribution. For example, if the filler is 75
When blended by volume or more, it is desirable that 70% by weight or more of the particles be spherical particles, which are distributed over a wide range of 0.1 to 80 μm. Since such a filler tends to have a close-packed structure, even if the amount is increased, the viscosity of the material does not increase so much that a composition having excellent fluidity can be obtained.

When the epoxy resin composition of the present invention is used as a molding material for sealing, it is preferable to add an anion exchanger from the viewpoint of improving the moisture resistance of an electronic component device having an element to be sealed. . The moisture resistance to be considered here refers to the humidity resistance of an electronic component device such as an IC package, and in particular, a bias-type high-temperature high-humidity test, HAST (HighlyAcid
The target is a moisture resistance test under voltage application such as a celerated humidity and stress test. Most of the failure modes generated in these moisture resistance tests are disconnections due to corrosion of aluminum wiring formed on IC elements. The epoxy resin of component (A) and the phenol resin of component (B) of the present invention Good moisture resistance reliability can be obtained by using an epoxy resin composition comprising a combination of a curing accelerator of component (C) and a specific amount of inorganic filler of component (D).
However, the addition of an anion exchanger is effective for obtaining more excellent voltage application type moisture resistance. In the case of the voltage application type moisture resistance test, the aluminum wiring on the anode side is particularly susceptible to corrosion, and the following phenomena can be considered as the cause. When water is present, the wiring or bonding pad on the anode side is subjected to anodic oxidation by oxygen generated by the electrolysis of water, and a stable aluminum oxide film is formed on the surface, so that aluminum corrosion should not proceed. However, the presence of a small amount of halogen ions such as chlorine solubilizes the aluminum oxide film, resulting in pitting corrosion in which the underlying aluminum is dissolved. Since the pitting corrosion on the anode side progresses faster than the grain boundary corrosion on the cathode side, in the voltage application type moisture resistance test, the corrosion of the aluminum wiring on the anode side proceeds first and becomes defective. Therefore, in order to prevent corrosion on the anode side, it is effective to add an anion exchanger capable of capturing a trace amount of halogen ions.

The anion exchanger that can be used in the present invention is not particularly limited, but hydrotalcites represented by the following formula (VII),

Embedded image Mg _1-x Al _x (OH) ₂ (CO ₃ ) _{x / 2} · mH ₂ O (VII) (0 <x ≦ 0.5, n is a positive number) Magnesium, aluminum, titanium, zirconium,
A hydrated oxide of an element selected from bismuth is preferred, and these may be used alone or in combination of two or more.

Hydrotalcites are trapped by replacing an anion such as a halogen ion with CO ₃ in the structure, and the halogen ion incorporated in the crystal structure is about 3
It is a compound that has the property of not desorbing at 50 ° C. or higher until the crystal structure is broken. An example of hydrotalcites having such properties is Mg ₆ A produced as a natural product.
l ₂ (OH) ₁₆ CO ₃ · 4H ₂ O or Mg _4.3 A as a synthetic product
l ₂ (OH) _12.6 CO ₃ · mH ₂ O and the like. In addition, the epoxy resin composition of the present invention has an effect that the extract of the cured product using pure water is p
H value of 3 to 5 and acidity. Therefore, although the environment is susceptible to corrosion for aluminum, which is an amphoteric metal, hydrotalcites also have the effect of adsorbing acids, and therefore have the effect of bringing the extract closer to neutrality. It can be inferred that the addition of sites is a factor that works effectively to prevent aluminum corrosion.

Hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth, and antimony can also be captured by replacing halogen ions with hydroxide ions, and these ion exchangers are excellent on the acidic side. Shows ion exchange capacity. As for the sealing epoxy resin molding material of the present invention, since the extract is on the acidic side as described above, these hydrated oxides are also particularly effective in preventing aluminum corrosion. For example, MgOnH
₂ O, Al ₂ O ₃ nH ₂ O, TiO ₂ nH ₂ O, ZrO ₂ nH ₂
O, Bi ₂ O ₃ nH ₂ O, and hydrated oxides such as Sb ₂ O ₅ nH ₂ O are exemplified.

The blending amount of these anion exchangers is not particularly limited as long as it is a sufficient amount to capture anions such as halogen ions. It is preferably set in the range of 0.1 to 30 parts by weight, more preferably 1 to 5 parts by weight.

The epoxy resin composition of the present invention may contain epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, as a coupling agent for enhancing the adhesiveness between the resin component and the filler as required.
Known additives such as various silane compounds such as vinyl silane, titanium compounds, aluminum chelates, and aluminum / zirconium compounds can be used.
Further, a known coloring agent such as carbon black, an organic dye, an organic pigment, titanium oxide, lead red, and red iron oxide may be added.

A release agent may be added to the epoxy resin composition of the present invention in order to have good releasability from a mold during molding. As the release agent, it is preferable to add 0.01 to 10 parts by weight of an oxidized or non-oxidized polyolefin to 100 parts by weight of the epoxy resin (A), more preferably 0.1 to 10 parts by weight. -5 parts by weight.
If the amount is less than 0.01 parts by weight, sufficient releasability cannot be obtained, and if it exceeds 10 parts by weight, the adhesiveness may be impaired. Examples of the oxidized or non-oxidized polyolefin include low molecular weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series manufactured by Hoechst. Further, as other release agents, for example, carnauba wax, montanic acid ester,
Examples thereof include montanic acid and stearic acid, which may be used alone or in combination of two or more. When these other release agents are used in addition to the oxidized or non-oxidized polyolefin, the mixing ratio thereof is usually 0.1 to 100 parts by weight of the epoxy resin (A). The amount is preferably 1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight.

A flame retardant may be added to the epoxy resin composition of the present invention in order to impart flame retardancy to the electronic component device. Examples of the flame retardant include known organic or inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, and metal hydroxides. Among them, a brominated epoxy resin and antimony trioxide are preferable.
These flame retardants are preferably blended in an amount of 1 to 30 parts by weight based on 100 parts by weight of the epoxy resin (A).
More preferably, it is 2 to 15 parts by weight. Further, as other additives, a stress relieving agent such as silicone oil or silicone rubber powder can be blended as required.

The resin composition of the present invention can be prepared by any method as long as the various components can be uniformly dispersed and mixed. As a general method, a predetermined amount of components is sufficiently mixed with a mixer or the like. After mixing, melt-kneading with a mixing roll, an extruder or the like, then cooling and pulverizing may be mentioned. For example, a predetermined amount of the above-described components can be uniformly stirred and mixed, kneaded with a kneader, roll, extruder, or the like that has been previously heated to 70 to 140 ° C., cooled, and pulverized.
It is easy to use if it is tableted with dimensions and weight that match the molding conditions.

As an electronic component device obtained by encapsulating the device with the epoxy resin composition obtained by the present invention, a semiconductor device is fixed on a lead frame, and terminal portions (bonding pads, etc.) and a lead portion of the device are connected. A common resin-sealed IC package or the like, which is connected by wire bonding or bumps and then sealed by transfer molding or the like using an epoxy resin composition, may be mentioned. For example, DIP (Dual Inline Package), PLCC (Pl
astic Leaded Chip Carrier), QFP (QuadFlat Pack)
age), SOP (Small Outline Package), SOJ (Sm
all Outline J-lead package), TSOP (Thin Small)
Outline Package), TQFP (ThinQuad Flat Packag)
e) and the like, and particularly when applied to an electronic component device mounted on a wiring board by a surface mounting method, excellent reliability can be exhibited. In the case of the above-described resin-sealed package having leads (external connection terminals), the elements to be sealed are transistors, thyristors, ICs, and LSs.
Not only semiconductor devices such as I and diodes, but also resistors, resistor arrays, capacitors, switches such as polyswitches, etc., and the epoxy resin composition of the present invention has excellent reliability for these devices. In addition to the above, it is possible to obtain excellent reliability for a hybrid IC in which various elements and electronic components are mounted on a ceramic substrate and then entirely sealed. Furthermore, after mounting the element on the surface of the organic substrate on which the terminals for wiring board connection are formed on the back surface and connecting the element and the wiring formed on the organic substrate by bump or wire bonding, using an epoxy resin composition BGA (Ball Grid) with elements sealed
Excellent reliability can also be obtained for electronic component devices such as an Array) and a CSP (Chip Size Package). It can also be used effectively for manufacturing printed circuit boards. As a method for sealing an electronic component device using the resin composition obtained by the present invention, a low-pressure transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.

[0030]

EXAMPLES Next, examples of the present invention will be described, but the scope of the present invention is not limited to these examples. Examples 1 to 12 and Comparative Examples 1 to 13 Epoxy equivalents of 196 and melting point of 106 were used as epoxy resins.
Biphenyl skeleton type epoxy resin (epoxy resin 1:
Yuka Shell Epoxy Co., Ltd., YX-4000H), diphenylmethane skeleton type epoxy resin having an epoxy equivalent of 192 and a melting point of 79 ° C. (Epoxy resin 2: Nippon Steel Chemical Co., Ltd., ESLV-8)
0XY), an epoxy equivalent of 192, a softening point of 80 ° C., a brominated bisphenol A type epoxy resin having a bromine content of 48% by weight (brominated epoxy 1), an epoxy equivalent of 393, and a softening point of 8
Brominated bisphenol A with 0 ° C and bromine content of 48% by weight
Type epoxy resin (brominated epoxy 2), phenol aralkyl resin having a hydroxyl equivalent of 176 and a softening point of 70 ° C. as a curing agent (curing agent 1: manufactured by Mitsui Chemicals, Inc., Millex XL)
-225), a biphenyl skeleton phenol novolak resin having a hydroxyl equivalent of 199 and a softening point of 89 ° C (curing agent 2: MEH-7851 manufactured by Meiwa Kasei Co., Ltd.), a hydroxyl equivalent of 197, and a softening point of 79
Naphthol phenol novolak resin (curing agent 3:
(Nippon Steel Chemical Co., Ltd., SN-180). 1, 3, 5,
7, 10, 14, 20, 22, and triphenylphosphine (accelerator A), an addition reaction product of triphenylphosphine with p-benzoquinone (accelerator B), and tri (p-tolyl) as a curing accelerator in Comparative Examples. Addition product of phosphine and p-benzoquinone (promoter C), phenol novolak salt of 1,8-diazabicyclo [5.4.0] undecene-7 (U-CAT SA-841 manufactured by San Apro Co., Ltd.) (promoted) Agent D), fused silica powder was used as an inorganic filler, and γ-glycidoxypropyltrimethoxysilane, carnauba wax, antimony trioxide, and carbon black were used as coupling agents as other additives. Table 3
Roll kneading was performed under the conditions of a kneading temperature of 80 to 90 ° C. and a kneading time of 15 minutes.
Epoxy resin compositions of Comparative Examples 1 to 13 were obtained.

[0031]

[Table 2]

[0032]

[Table 3]

The epoxy resin compositions obtained in Examples and Comparative Examples were subjected to the following various property tests (1) to (6). The results are shown in Tables 4 and 5. (1) Spiral flow 180 ° C., 7 Mpa, 90 according to EEMI1-66
The flow length (in inches) when molded under the condition of seconds was measured. (2) Hot Hardness (Shore D) The Shore D hardness of a test piece (50 mmφ × 3 mmt) when molded under the conditions of 180 ° C., 7 MPa, and 90 seconds was measured. (3) Hot Hardness During Moisture Absorption (Shore D) The hot hardness was measured in the same manner as in (2) above, using the resin composition left for 72 hours at 25 ° C./50% RH. (4) PIQ peel adhesive strength (N / m): width 10 mm, thickness 5 μ with 10 μm PIQ layer formed
180 ° C. on the PIQ layer using
A plate test piece of 3 mmt was formed under the condition of 7 Mpa,
The peel strength was measured at a speed of 50 mm / min in the ° direction. (5) Moisture resistance TEG with aluminum wiring of 10 μm line width and 1 μm thickness
SOP package (18.3 ×
8.4 × 2.6 mm, 28 pins, 42 alloy lead frame) was after-cured at 175 ° C. for 5 hours, and then heated at 85 ° C. /
Humidified at 85% RH for 72 hours. Then 215 ° C / 90
A second VPS reflow process was performed, and a 2 atm PCT process was performed for a predetermined time to evaluate the presence or absence of disconnection due to aluminum wiring corrosion. (6) Number of internal voids generated 8 × 10 molded under the conditions of 180 ° C., 7 MPa, and 90 seconds.
(Mm) 80-pin, 14 × 20 ×
A 2t (mm) QFP package (the average length of the gold wire connecting the silicon chip and the lead frame was 6 mm) was observed with a soft X-ray fluoroscope, and the number of voids having a size of 0.1 mmφ or more was counted.

[0034]

[Table 5]

[0035]

[Table 6]

As shown in Examples 1 to 8, the resin composition of the present invention exhibited a spiral flow of about 40 inches, a hot hardness of about 80, a hot hardness of 70 or more, and a PIQ peel adhesive strength. , Moisture resistance reliability and the number of voids generated. On the other hand, in the comparative example not including the curing accelerator of the present invention, the resin composition of Comparative Example 1 had low fluidity and extremely generated voids. In addition, the resin composition of Comparative Example 2 was inferior in heat hardness at the time of moisture absorption, the resin composition of Comparative Example 3 was inferior in fluidity and PIQ peel adhesion, and the resin composition of Comparative Example 4 was excellent in fluidity and heat at moisture absorption. The hardness and the number of voids were inferior. Furthermore, the resin composition of Comparative Example 5 was inferior in PIQ peel adhesion and moisture resistance reliability. Further, from Examples and Comparative Examples in which different resin compositions were examined, the resin compositions of Examples 9 to 12 according to the present invention were compared with the resin compositions of Comparative Examples 6 to 9 in terms of hot hardness and moisture absorption. Excellent hot hardness,
Compared with the resin compositions of Comparative Examples 10 to 13, they were superior in terms of PIQ peel adhesion, moisture resistance reliability, and the number of voids generated.

[0037]

As shown in the examples, the epoxy resin composition of the present invention is particularly suitable for semiconductors because it has no voids, and is excellent in curability when absorbing moisture, adhesion to a passivation film, and moisture resistance. It is suitably used for sealing applications, and its industrial value is great.

Continued on the front page F-term (reference) 4J002 CC042 CC062 CC282 CD011 CD021 CD041 CD051 CD061 CD101 CD131 CD141 CD171 CE002 DE078 DE098 DE138 DE148 DE238 DF018 DJ008 DJ018 DJ038 DJ048 DJ058 DK008 DL008 EN047 EN107 EN127 EU117 EW146 EW147 017 017 017 017 017 AD08 AE05 AF05 AF06 AF10 AG06 AG07 AH07 DD07 FB07 FB08 4M109 AA01 BA01 BA03 CA21 EA03 EA06 EB03 EB04 EB06 EB07 EB08 EB09 EB12 EB16 EB19 EC03 EC05

Claims (6)

[Claims] 1. An epoxy resin having two or more epoxy groups in one molecule, (B) a phenolic resin having two or more phenolic hydroxyl groups in one molecule, (C) a phenolic resin having the following formula (I): A curing accelerator represented by the formula: (Here, R ¹ and R ² are selected from hydrogen, an alkyl group having 1 to 6 carbon atoms and an alkoxyl group having 1 to 6 carbon atoms, and may be the same or different except when both are hydrogen. R
³ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and m represents 1 or 2. ) As an essential component. 2. The epoxy resin composition according to claim 1, which contains 55% by volume or more of an inorganic filler (D) based on the whole composition. 3. An equivalent ratio ((B) / (A)) of an epoxy group of the epoxy resin (A) to a phenolic hydroxyl group of the phenol resin (B) is from 0.5 to 2. Item 3. The epoxy resin composition according to item 1 or 2. 4. The epoxy resin composition according to claim 1, wherein the component (A) contains an epoxy resin represented by the following formula (II) and / or (III). Embedded image (Here, each of the four R ⁴ and R ⁵ in the formula may be the same or different and represents hydrogen or a methyl group.) 5. The composition according to claim 1, wherein the component (B) contains at least one of the phenolic resins represented by the following formulas (IV), (V) and (VI). An epoxy resin composition according to any of the preceding claims. Embedded image (Here, X, Y, and Z show 0-10.) 6. An electronic component device comprising an element sealed with the epoxy resin composition according to any one of claims 1 to 5.