JP2001233944A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which shows excellence in moldability, fire retarding property, storage at an ambient temperature and solder crack resistance. SOLUTION: An epoxy resin composition for sealing a semiconductor contains as essential components (A) an epoxy resin including a glycidyl-etherized 4,4'- dihydroxy-3,3',5,5'-tetramethylbiphenyl (a) and a glycidyl-etherized bis (3, 5- dimethyl-4-hydroxyphenyl)methane (b), (B) a phenol resin represented by formula (1), (C) whole inorganic materials and (D) a curing accelerator which is a molecular associate of a tetra-substituted phosphonium (P) with a compound having 2 or more phenolic hydroxyl groups in a molecule (Q) and a conjugated base of the compound having 2 or more phenolic hydroxyl groups in a molecule (Q), the conjugated base being a phenoxide type compound obtained by removing one hydrogen from the compound having 2 or more phenolic hydroxyl groups in a molecule (Q), wherein the weight ratio of (a) to (b) (a)/(b) is 1/3 to 3 and the content of the whole inorganic materials is 87 to 94 wt.% based on the whole epoxy resin composition. (wherein the average value of n is 1 to 10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to moldability, flame retardancy,
The present invention relates to an epoxy resin composition for semiconductor encapsulation having excellent room temperature storage properties and solder stress resistance, and a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, semiconductor devices such as diodes, transistors, and integrated circuits are mainly sealed with an epoxy resin composition. These epoxy resin compositions usually impart flame retardancy. Usually for bromine-containing organic compounds,
And antimony compounds such as antimony trioxide and antimony tetroxide. However, development of an epoxy resin composition excellent in flame retardancy without using a bromine-containing organic compound and an antimony compound is desired from the viewpoint of environment and hygiene. In addition, when a semiconductor device is mounted on a printed circuit board, lead-containing solder (tin-lead alloy) is used. Similarly, lead-containing solder (tin-lead alloy) is used from the viewpoint of environment and sanitation. It is desired not to use it. The melting point of lead-containing solder (tin-lead alloy) is 18
At 3 ° C., the soldering temperature during mounting is 220 to 240 ° C. On the other hand, a lead-free solder typified by a tin-silver alloy has a high melting point and a temperature of 26 ° C. during the soldering process.
Since the temperature is about 0 ° C., development of an epoxy resin composition having more excellent solder stress resistance is desired.

In order to improve flame retardancy and solder stress resistance, it is necessary to increase the amount of an inorganic filler and reduce the content of a resin component. One of the methods is to use a low-viscosity crystalline epoxy resin. Is used. At present, an epoxy resin composition using a low-viscosity crystalline epoxy resin without using a flame retardant and highly filled with an inorganic filler or an epoxy resin composition using a highly flame-retardant resin, and various flame retardants are used. The epoxy resin composition used has been proposed, but no epoxy resin composition that completely satisfies good moldability or solder stress resistance has not yet been proposed. Furthermore, in the step of sealing a semiconductor device with an epoxy resin composition, it is required to shorten the molding time as one of means for increasing production efficiency. For this purpose, rapid curing at the time of molding is required. When a conventional curing accelerator is added in an amount sufficient to achieve rapid curing at the time of molding, there is a problem that the storage stability of the epoxy resin composition at room temperature is extremely reduced.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a bromine-containing organic compound by using a low melt viscosity epoxy resin to make the inorganic filler more highly filled than ever before and using a phenol resin having excellent flame retardancy. By using a curing accelerator containing no antimony compound and not exhibiting catalytic activity at room temperature, it is possible to stably store the epoxy resin composition for a long period of time without curing progressing at room temperature, Sometimes, when heated, a curing reaction develops, resulting in good moldability, flame retardancy, high-temperature storage characteristics,
Another object of the present invention is to provide an epoxy resin composition for semiconductor encapsulation having excellent solder stress resistance, and a semiconductor device obtained by encapsulating a semiconductor element using the epoxy resin composition.

[0005]

The present invention provides (A) 4,
Epoxy which is a glycidyl etherified product of 4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl (a) and a glycidyl etherified product of bis (3,5-dimethyl-4-hydroxyphenyl) methane (b) resin,
(B) a phenolic resin represented by the general formula (1), (C)
(D) Formula (2), Formula (3), tetra-substituted phosphonium (P) and a compound (Q) having two or more phenolic hydroxyl groups in one molecule, and (D) a compound having two or more phenolic hydroxyl groups in one molecule. A molecular conjugate (M) of a compound (Q) having at least two phenolic hydroxyl groups in one molecule of the compound (Q) having at least two phenolic hydroxyl groups in the molecule. One or more curing accelerators selected from phenoxide-type compounds as essential components, the weight ratio (a / b) of (a) to (b) is 1/3 to 3, and all inorganic substances are all epoxy resin compositions 87 to 94% by weight of the epoxy resin composition for semiconductor encapsulation, and (A) 4,4'-dihydroxy-3,3 ', 5,5'-
An epoxy resin which is a glycidyl etherified product of tetramethylbiphenyl (a) and a glycidyl etherified product of bis (3,5-dimethyl-4-hydroxyphenyl) methane (b); (B) a phenolic resin represented by the general formula (1) , (C) all inorganic substances, (D) formula (2), general formula (3), tetra-substituted phosphonium (P) and compounds (Q) and 1 having two or more phenolic hydroxyl groups in one molecule.
A compound (M) with a conjugate base of a compound (Q) having two or more phenolic hydroxyl groups in the molecule, wherein the conjugate base has two or more phenolic hydroxyl groups in one molecule (Q ), One or more curing accelerators selected from phenoxide-type compounds from which one hydrogen has been removed, and the weight ratio (a / b) between (a) and (b) is 1/3.
-3, the total amount of inorganic substances is 87-94 in the total epoxy resin composition.
% By weight, and the content of the bromine-containing organic compound and the antimony compound is 1000 ppm or less for each flame retardant component, and a semiconductor element-encapsulating epoxy resin composition. A semiconductor device comprising:

Embedded image (N is an average value and a positive number from 1 to 10)

[0006]

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[0007]

Embedded image (Wherein, X ₁ , X ₂ , X ₃ and X ₄ are monovalent organic acids or monovalent aliphatic groups having an aromatic ring or a heterocyclic ring, even if they are the same as each other) Y ₁ , Y ₂ , Y ₃ and Y ₄ are monovalent organic acids or monovalent aliphatic groups having an aromatic or heterocyclic ring,
At least one of them is a group obtained by releasing one proton from a proton donor having at least one proton that can be released outside the molecule, and they may be the same or different. )

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The epoxy resin used in the present invention comprises:
Glycidyl ether of 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl (a) and glycidyl ether of bis (3,5-dimethyl-4-hydroxyphenyl) methane (b) Yes, it is a crystalline solid at room temperature, but has the property of becoming a very low viscosity liquid when melted by heating. This makes it possible to increase the amount of the inorganic filler, and thus reduce the moisture absorption of the cured product of the epoxy resin composition. Therefore, a semiconductor device sealed with a resin composition using these epoxy resins can have high reliability even under a soldering process at the time of mounting.

The epoxy resin used in the present invention is 4,4 ′
Glycidyl etherified product of dihydroxy-3,3 ′, 5,5′-tetramethylbiphenyl (a) and bis (3,3)
The weight ratio (a / b) of 5-dimethyl-4-hydroxyphenyl) methane to the glycidyl etherified product (b) is 1 /
The range of 3 to 3 is preferred, and more preferably 1/2 to 2. If the ratio is out of this range, characteristics such as excellent fluidity, curability, and resistance to solder stress cannot be sufficiently exhibited, which is not preferable. The method for mixing the resins is not particularly limited. Glycidyl etherified product of 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl (a)
And bis (3,5-dimethyl-4-hydroxyphenyl)
It may be used in combination with another epoxy resin as long as the properties of the epoxy resin which is the glycidyl etherified product of methane (b) are not impaired. When used in combination, all monomers, oligomers and polymers having an epoxy group in the molecule may be used. Examples of the epoxy resin to be used in combination include a naphthalene-type epoxy resin, a dicyclopentadiene-modified phenol-type epoxy resin, and a triphenol-type epoxy resin. These may be used alone or in combination.

The phenolic resin represented by the general formula (1) used in the present invention has a methylene-biphenyl skeleton-methylene structure, and a cured product of the resin composition using the phenolic resin has a low elastic modulus, Also, since it has low moisture absorption, it has excellent adhesion to metals such as lead frames and semiconductor elements such as silicon chips. It is desirable that n = 1 to 10, and the weight ratio of n = 1 to 3 be 50% or more. When the weight ratio of n = 4 or more increases, the resin viscosity increases and the fluidity decreases. By adjusting the amount of the phenol resin used, the solder stress resistance can be maximized. In order to bring out the effect of resistance to soldering stress, it is desirable that the phenolic resin represented by the general formula (1) be contained in an amount of 30% by weight or more, preferably 50% by weight or more, based on the total amount of the phenolic resin. If the amount is less than 30% by weight, the solder stress resistance may be insufficient. The phenol resin represented by the general formula (1) used in the present invention may be used in combination with another phenol resin as long as the properties of the phenol resin are not impaired. When used in combination, all monomers, oligomers and polymers having a phenolic hydroxyl group in the molecule may be used. Examples of the phenol resin used in combination include a phenol novolak resin, a cresol novolak resin, a dicyclopentadiene-modified phenol resin, a xylylene-modified phenol resin, a terpene-modified phenol resin, a triphenolmethane compound, and the like, and these may be used alone or in combination. . The equivalent ratio of the epoxy group of all epoxy resins used in the present invention to the phenolic hydroxyl group of all phenolic resins is preferably 0.5 to 2, and more preferably 0.7 to 1.5. If the ratio is out of the range of 0.5 to 2, the moisture resistance, the curability and the like are undesirably reduced.

The type of the inorganic filler used in the present invention is not particularly limited, and those generally used for a sealing material can be used. For example, fused silica,
Examples thereof include fused spherical silica, crystalline silica, secondary aggregated silica, alumina, titanium white, and aluminum hydroxide. Particularly preferred is fused spherical silica. As the shape of the fused spherical silica, it is preferable that the shape is infinitely spherical and the particle size distribution is broad in order to improve fluidity. The term “all inorganic substances” as used in the present invention is a sum of the inorganic filler, an antimony compound used as a flame retardant, and an inorganic substance such as an inorganic ion exchanger as an ion scavenger.
The content of all inorganic substances is 8% of the total epoxy resin composition.
7-94% by weight is preferred. If it is less than 87% by weight, low moisture absorption is not obtained and solder stress resistance becomes insufficient, and bromine-containing organic compounds such as brominated orthocresol novolak type epoxy resin and brominated bis A type epoxy resin and antimony trioxide, Unless a flame retardant such as an antimony compound such as antimony tetroxide is added, the flame retardancy is insufficient, which is not preferable. If the content is more than 94% by weight, the fluidity is reduced, and there is a possibility that incomplete filling or the like may occur during molding, or an inconvenience such as a gold wire deformation in the semiconductor device due to an increase in viscosity may occur. In the present invention, the flame retardant of the bromine-containing organic compound and the antimony compound is 100% for each flame retardant component.
0 ppm or less. Even if the flame retardant is not intentionally added, it is difficult to set the level mixed in the raw materials and the production stage to 0 ppm for economic reasons.
And 0 ppb, the function of the present invention is effective. It is preferable that the inorganic filler used in the present invention is sufficiently mixed in advance. If necessary, the inorganic filler may be treated in advance with a coupling agent, an epoxy resin or a phenol resin, and may be used. The method of the treatment includes a method of removing the solvent after mixing with a solvent or a method of directly filling the inorganic filler. There is a method of adding to a material and treating using a mixer.

The curing accelerator represented by the formula (2) used in the present invention does not show catalytic activity at normal temperature, so that the curing reaction of the epoxy resin composition does not proceed, and the catalytic activity is exhibited at high temperature during molding. Once exhibited, they exhibit a higher catalytic activity than conventional curing accelerators, and have the characteristic of highly curing epoxy resin compositions. The curing accelerator represented by the general formula (3) used in the present invention comprises phosphonium borate. However, in the general formula (3), X ₁ , X ₂ , X ₃ and X ₄ of the phosphonium group are a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring. They may be the same or different. Such phosphonium groups include, for example, tetraphenylphosphonium, tetratolylphosphonium,
Tetraethylphenylphosphonium, tetramethoxyphenylphosphonium, tetranaphthylphosphonium, tetrabenzylphosphonium, ethyltriphenylphosphonium, n-butyltriphenylphosphonium, 2-hydroxyethyltriphenylphosphonium, trimethylphenylphosphonium, methyldiethylphenylphosphonium, methyldiallylphenylphosphonium And tetra-n-butylphosphonium. In the general formula (3), X ₁ , X ₂ , X ₃ and X ₄ are particularly preferably a monovalent organic group having an aromatic ring, and the melting point of the phosphonium borate represented by the general formula (3) is Although not particularly limited, 25 from the viewpoint of uniform dispersion.
It is preferably 0 ° C. or lower. In particular, a phosphonium borate having a tetraphenylphosphonium group has good compatibility with a thermosetting resin and can be suitably used.

In the general formula (3), Y ₁ , Y ₂ , Y ₃ and Y ₄ of the borate group are a monovalent organic group or a monovalent aliphatic group having an aromatic ring or a heterocyclic ring. Is at least one of the proton donors having at least one proton that can be released outside the molecule.
This is a group which is released individually, and Y ₁ , Y ₂ , Y ₃ and Y ₄ may be the same or different. Examples of such a proton donor that provides a borate group include aromatic acids such as benzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, trimellitic acid, pyromellitic acid, and 2,6-naphthalenedicarboxylic acid. Phenolic compounds such as carboxylic acid, phenol, biphenol, bisphenol A, bisphenol F, 1-naphthol, 2-naphthol, and polyphenol are good and can be suitably used. When the curing accelerator represented by the general formula (3) used in the present invention is mixed with the epoxy resin composition, it does not show catalytic activity at room temperature, so that the curing reaction of the epoxy resin does not progress, and the The catalyst activity is exhibited at a high temperature, and once developed, shows a higher catalytic activity than conventional curing accelerators, and highly cures the epoxy resin composition.

The compound (Q) having two or more phenolic hydroxyl groups in one molecule and the tetra-substituted phosphonium (P) used in the present invention, and two or more phenolic hydroxyl groups in one molecule.
A compound (M) with a conjugate base of a compound (Q) having at least two phenolic hydroxyl groups, wherein the compound is a phenoxide-type compound obtained by removing one hydrogen from the compound (Q) having at least two phenolic hydroxyl groups. The substituent of the tetra-substituted phosphonium (P), which is one of the constituents, is not limited, and the substituents may be the same or different. For example, a tetra-substituted phosphonium ion having a substituted or unsubstituted aryl or alkyl group as a substituent is preferable because it is stable against heat and hydrolysis. Specifically, tetraphenylphosphonium,
Tetratolylphosphonium, tetraethylphenylphosphonium, tetramethoxyphenylphosphonium, tetranaphthylphosphonium, tetrabenzylphosphonium, ethyltriphenylphosphonium, n-butyltriphenylphosphonium, 2-hydroxyethyltriphenylphosphonium, trimethylphenylphosphonium,
Examples thereof include methyldiethylphenylphosphonium, methyldiallylphenylphosphonium, and tetra-n-butylphosphonium.

The compound (Q) having two or more phenolic hydroxyl groups in one molecule, which is a component of the molecular aggregate (M) used in the present invention, includes, for example, bis (4-hydroxy-3,5- Dimethylphenyl) methane (commonly known as tetramethylbisphenol F), 4,4'-sulfonyldiphenol, 4,4'-isopropylidenediphenol (commonly known as bisphenol A), bis (4-hydroxyphenyl) methane, bis (2-hydroxy Phenyl) methane, (2-hydroxyphenyl) (4-hydroxyphenyl) methane and bis (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, (2-hydroxyphenyl) (4-hydroxyphenyl) ) A mixture of three types of methane (for example, bisphenol manufactured by Honshu Chemical Industry Co., Ltd.) -D) and the like; dihydroxybenzenes such as 1,2-benzenediol, 1,3-benzenediol and 1,4-benzenediol; trihydroxybenzenes such as 1,2,4-benzenetriol; Various isomers of dihydroxynaphthalenes such as 2,6-dihydroxynaphthalene, 2,2 ′
-Phenol, compounds such as various isomers of biphenols such as 4,4'-biphenol, phenol novolak resins, phenol aralkyl resins and the like. Further, the conjugate base as another component is a phenoxide-type compound obtained by removing one hydrogen from the compound (Q).

The molecular-molecule aggregate (M) of the present invention has a phosphonium-phenoxide-type salt in its structure as described above, but differs from the phosphonium-organic acid anion salt-type compound in the prior art in that In the molecular aggregate (M) of the present invention, a higher-order structure due to hydrogen bonding surrounds ionic bonds. In the salt of the prior art, the reactivity is controlled only by the strength of the ionic bond. On the other hand, in the molecular aggregate (M) of the present invention, the enclosing by the higher order structure of the anion protects the active site at normal temperature. While doing
In the molding stage, the active sites are exposed by the collapse of the higher-order structure, and a so-called latency that expresses reactivity is imparted. The method for producing the molecular aggregate (M) of the present invention is not limited at all, but two typical methods can be mentioned. The first is to react a tetra-substituted phosphonium / tetra-substituted borate (Z) with a compound (Q) having two or more phenolic hydroxyl groups in one molecule at a high temperature, and then further to a boiling point of 60 ° C. or more. Is a method in which a thermal reaction is carried out in a solvent of The second is a method in which a compound (Q) having two or more phenolic hydroxyl groups in one molecule is reacted with an inorganic base or an organic base and a tetra-substituted phosphonium halide.

The substituent of the tetra-substituted phosphonium halide to be used is not limited at all, and the substituents may be the same or different. For example, a tetra-substituted phosphonium ion having a substituted or unsubstituted aryl or alkyl group as a substituent is preferable because it is stable against heat and hydrolysis. Specifically, tetraphenylphosphonium, tetratolylphosphonium, tetraethylphenylphosphonium, tetramethoxyphenylphosphonium, tetranaphthylphosphonium, tetrabenzylphosphonium, ethyltriphenylphosphonium, n
-Butyltriphenylphosphonium, 2-hydroxyethyltriphenylphosphonium, trimethylphenylphosphonium, methyldiethylphenylphosphonium, methyldiallylphenylphosphonium, tetra-n-butylphosphonium and the like. Examples of the halide include chloride and bromide, which may be selected from the properties of the tetra-substituted phosphonium halide, such as the price and moisture absorption, and the availability, and any of them may be used. In addition, triphenylphosphine, 1,8-diazabicyclo (5,
There is no problem when used in combination with other curing accelerators such as (4,0) undecene-7 and 2-methylimidazole.

The epoxy resin composition of the present invention comprises (A)
In addition to the component (D), if necessary, an inorganic ion exchanger such as bismuth oxide hydrate, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a coloring agent such as carbon black and red iron, silicone oil, A low stress component such as silicone rubber, a natural wax, a synthetic wax, a higher fatty acid and a metal salt thereof, or a mold release agent such as paraffin, and various additives such as an antioxidant may be appropriately compounded. The epoxy resin composition of the present invention comprises (A)
(D) A component, other additives, etc. are mixed at normal temperature using a mixer, melt-kneaded with a kneader such as a roll, kneader, extruder or the like, cooled, and pulverized. In order to manufacture a semiconductor device by encapsulating an electronic component such as a semiconductor element using the epoxy resin composition of the present invention, it is sufficient to cure and mold by a molding method such as a transfer mold, a compression mold, and an injection mold.

[Synthesis of Molecular Association (M)] Synthesis Example 1 300 g (1.5 mol) of bisphenol FD (corresponding to compound (Q)) manufactured by Honshu Chemical Industry Co., Ltd., and tetraphenylphosphonium tetra Phenyl borate (Z) 32
9 g (0.5 mol) was charged into a 3 L separable flask and reacted at 200 ° C. for 3 hours. The amount of benzene distilled in this reaction was 97% by weight of the theoretical amount (that is, the benzene distillation rate was 97%). The crude product from this reaction is finely pulverized, charged into a separable flask, and 2-propanol is added in an amount 3 times the charged weight of the crude product, and the internal temperature is 82.4 ° C.
(Boiling point temperature of 2-propanol) for 1.5 hours. Thereafter, most of the 2-propanol was removed, and a low-boiling component was further removed under heating and reduced pressure. The obtained product was designated as compound (M-1). The solvent is heavy methanol,
(M-1) was measured by ¹ H-NMR. 4.8p
The peaks around pm and around 3.3 ppm are the peaks of the solvent, and the peak group around 6.4 to 7.1 ppm is the starting material bisphenol F [moles (a) per mole of bisphenol (P)] and the bisphenol F A phenoxide-type conjugated base [molar number (b) per mole of (P)] from which one hydrogen has been removed, 7.6 to 8.0 p
The peak group near pm is assigned to the phenyl proton of the tetraphenylphosphonium group, and from their area ratio,
The molar ratio was calculated to be [(a + b) / (P)] = 2.2 / 1.

Synthesis Example 2 In a 5-liter separable flask, 300 g of bisphenol FD (corresponding to compound (Q)) manufactured by Honshu Chemical Industry Co., Ltd.
(1.5 mol), 314 g (0.75 mol) of tetraphenylphosphonium bromide manufactured by Hokuko Chemical Industry Co., Ltd.,
3000 g of methanol was charged and completely dissolved. A methanol / water mixed solution containing 30 g of sodium hydroxide was added dropwise thereto with stirring. A reprecipitation operation of dropping the obtained solution into a large amount of water was performed to obtain the target substance as a solid. The solid was taken out by filtration and dried to obtain a product, which was designated as compound (M-2). Further, the measurement was performed by ¹ H-NMR of (M-2) using heavy methanol as a solvent. The peaks around 4.8 ppm and 3.3 ppm are the peaks of the solvent, and the peak group around 6.4 to 7.1 ppm is the raw material bisphenol F [mol (a) based on 1 mol of (P)] and A phenoxide-type conjugate base obtained by removing one hydrogen from bisphenol F [the number of moles (b) per mole of (P)] phenyl proton, 7.6 to
The peak group around 8.0 ppm was assigned to the phenyl proton of the tetraphenylphosphonium group, and from the area ratio thereof, the molar ratio was calculated to be [(a + b) / (P)] = 2/1.

[0021]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The mixing ratio is by weight. Example 1 The following composition An epoxy resin containing a glycidyl etherified product of 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl as a main component (epoxy equivalent: 197 g / eq. 2.01 parts by weight Epoxy resin containing glycidyl ether of bis (3,5-dimethyl-4-hydroxyphenyl) methane as a main component (epoxy equivalent: 192 g / eq. 2.00 parts by weight Phenolic resin represented by formula (4) (hydroxyl equivalent: 203 g / eq) 4.19 parts by weight Fused spherical silica 90.00 parts by weight Curing accelerator represented by formula (2) 0.20 parts by weight Inorganic ion exchanger 0.50 parts by weight γ-glycidoxypropyltrimethoxysilane 0.30 parts by weight Carbon black 0.30 parts by weight The Runabawakkusu 0.50 parts by weight were mixed using a mixer at normal temperature, 2 at 70 to 120 ° C.
The mixture was kneaded using an axial roll, cooled and pulverized to obtain a resin composition. The obtained resin composition was evaluated by the following method. Table 1 shows the results.

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[0022]

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Evaluation method Spiral flow: Spiral flow was measured using a mold for measuring spiral flow according to EMMI-1-66 at a mold temperature of 175 ° C., an injection pressure of 70 kg / cm ² and a curing time of 2 minutes. The unit is cm. Curing Torque: Using a curast meter (manufactured by Orientec Co., Ltd., JSR curast meter IVPS type), a torque at a mold temperature of 175 ° C. and 90 seconds after the start of heating was determined.
The torque in the curast meter is a parameter of curability, and the larger the numerical value, the better the curability. The unit is kgf · cm. Storage at 25 ° C .: The spiral flow is measured after storing the resin composition at 25 ° C. for 3 days, and expressed as a percentage of the spiral flow immediately after the preparation of the resin composition. Flame retardancy: Mold using a transfer molding machine Temperature 17
A molded article having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm was molded at 5 ° C., an injection pressure of 75 kg / cm ² , and a curing time of 2 minutes, and subjected to a flame retardancy test according to UL-94. Solder stress resistance: tableting the resin composition, using a low pressure transfer molding machine, mold pressure 175 ° C, injection pressure 100 kg / cm ² , curing time 2 minutes, 80p
A QFP (thickness 1.5 mm, chip size 6 × 6 mm) was formed. Eight packages, which were post-cured at 175 ° C. for 8 hours, were processed at 85 ° C. and a relative humidity of 85% for 168 hours, and then subjected to IR reflow processing (260
° C). After the treatment, the presence of peeling and cracks in the inside was observed with an ultrasonic flaw detector, and the number of defective packages was counted. When the number of defective packages is n, n / 8
Is displayed. Table 1 shows the evaluation results.

Examples 2 to 6, Comparative Examples 1 to 7 Resin compositions were obtained in the same manner as in Example 1 according to the formulations in Tables 1 and 2, and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2. In Examples 2 and 6, and Comparative Examples 1 and 5, the curing accelerator of the formula (5) was used. DBU of Comparative Example 3
Is 1,8-diazabicyclo (5,4,0) undecene-7. In Comparative Examples 4 and 7, a paraxylylene-modified phenol resin (hydroxyl equivalent 174 g / eq) was used.

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[0025]

[Table 1]

[0026]

[Table 2]

[0027]

According to the present invention, it is possible to stably store at room temperature for a long period of time without curing progressing, and when heated during molding, a curing reaction is developed to show good moldability. An epoxy resin composition is obtained, and a semiconductor device using the same is excellent in flame retardancy and solder stress resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/49 C08K 5/49 5/55 5/55 C08L 63/02 C08L 63/02 65/00 65 / 00 H01L 23/29 H01L 23/30 R 23/31 F term (reference) 4J002 CD05W CE00X DE136 DE146 DJ016 EJ037 EJ077 EW177 EY017 FA086 FD016 FD14X FD157 4J036 AA02 AA05 AD07 AD08 DA01 DA02 DA04 DA05 DB06 FB08 GA09 AGA05A06 EA06 EB04 EB12 EB13

Claims (3)

[Claims] (A) 4,4′-dihydroxy-3,
Glycidyl etherified product of 3 ', 5,5'-tetramethylbiphenyl (a) and bis (3,5-dimethyl-4-
An epoxy resin which is a glycidyl etherified product of (hydroxyphenyl) methane (b), (B) a phenolic resin represented by the general formula (1), (C) all inorganic substances, (D) a formula (2), a general formula (3), Tetra-substituted phosphonium (P)
A compound (Q) having two or more phenolic hydroxyl groups in one molecule and a conjugate base (M) of a compound (Q) having two or more phenolic hydroxyl groups in one molecule, A conjugate base comprising at least one curing accelerator selected from phenoxide-type compounds obtained by removing one hydrogen from the compound (Q) having two or more phenolic hydroxyl groups in one molecule, and (a) (B) weight ratio (a /
b) is 1/3 to 3 and the total amount of inorganic substances is 87 to 94% by weight of the total epoxy resin composition. (A) 4,4′-dihydroxy-3,
Glycidyl etherified product of 3 ', 5,5'-tetramethylbiphenyl (a) and bis (3,5-dimethyl-4-
An epoxy resin which is a glycidyl etherified product of (hydroxyphenyl) methane (b), (B) a phenolic resin represented by the general formula (1), (C) all inorganic substances, (D) a formula (2), a general formula (3), Tetra-substituted phosphonium (P)
A compound (Q) having two or more phenolic hydroxyl groups in one molecule and a conjugate base (M) of a compound (Q) having two or more phenolic hydroxyl groups in one molecule, A conjugate base comprising at least one curing accelerator selected from phenoxide-type compounds obtained by removing one hydrogen from the compound (Q) having two or more phenolic hydroxyl groups in one molecule, and (a) (B) weight ratio (a /
b) is 1/3 to 3, all inorganics are 87 to 94% by weight of the total epoxy resin composition, and the bromine-containing organic compound and the antimony compound are 100% for each flame retardant component.
An epoxy resin composition for semiconductor encapsulation, wherein the content is 0 ppm or less. Embedded image (N is an average value and a positive number of 1 to 10) Embedded image (Wherein, X ₁ , X ₂ , X ₃ and X ₄ are monovalent organic acids or monovalent aliphatic groups having an aromatic ring or a heterocyclic ring, even if they are the same as each other) Y ₁ , Y ₂ , Y ₃ and Y ₄ are monovalent organic acids or monovalent aliphatic groups having an aromatic or heterocyclic ring,
At least one of them is a group obtained by releasing one proton from a proton donor having at least one proton that can be released outside the molecule, and they may be the same or different. ) 3. A semiconductor device comprising a semiconductor element encapsulated with the epoxy resin composition for semiconductor encapsulation according to claim 1 or 2.