JP2003268208A - Flame-retardant epoxy resin composition for semiconductor encapsulation and semiconductor device - Google Patents

Abstract

(57) Abstract: (A) Epoxy resin (B) Curing agent (C) Inorganic filler (D) Melting point represented by the following average composition formula (1): 110 ° C
A phosphazene compound having a temperature of at least 130 ° C. (Where a, b, n are 0 <a ≦ 0.05n, 1.90n
≦ b <2n, 2a + b = 2n, 3 ≦ n ≦ 6. A) a flame-retardant epoxy resin composition for semiconductor encapsulation, wherein the epoxy resin composition essentially comprises a bromide and an antimony compound. EFFECTS The flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is excellent in moldability, and can provide a cured product excellent in flame retardancy and moisture resistance reliability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a cured product which is excellent in moldability, flame retardancy and moisture resistance reliability, and does not contain bromide such as brominated epoxy resin or antimony compound such as antimony trioxide. The present invention relates to an epoxy resin composition for semiconductor encapsulation, and a semiconductor device encapsulated with a cured product of the resin composition.

[0002]

2. Description of the Related Art At present, semiconductor devices are mainly resin-sealed diodes, transistors, ICs, LSIs, and VLSIs. Epoxy resins are more moldable, adhesive, and electric than other thermosetting resins. Since the semiconductor device is excellent in properties, mechanical properties, moisture resistance, etc., it is common to seal the semiconductor device with an epoxy resin composition. Semiconductor devices are home appliances,
Since it is used everywhere in a living environment such as a computer, the semiconductor device is required to have flame retardancy in case of a fire.

In the epoxy resin composition for semiconductor encapsulation,
A halogenated epoxy resin and antimony trioxide are generally mixed in order to enhance flame retardancy. The combination of this halogenated epoxy resin and antimony trioxide has a large radical trap and air blocking effect in the gas phase,
As a result, a high flame retardant effect can be obtained.

However, the halogenated epoxy resin has a problem that it emits a toxic gas when it is burned, and antimony trioxide has powder toxicity, so in consideration of the effects on the human body and the environment, these flame retardants are used as resins. It is preferred to not include it at all in the composition.

In response to such requirements, as a substitute for the halogenated epoxy resin or antimony trioxide, conventionally, hydroxides such as Al (OH) ₃ and Mg (OH) ₂ and red phosphorus, phosphoric acid ester and the like have been used. Phosphorus flame retardants have been studied. However, since hydroxides such as Al (OH) ₃ and Mg (OH) ₂ have a low flame retardant effect, a large amount of hydroxide must be added to the epoxy resin composition in order to obtain a flame retardant composition. As a result, there is a problem in that the viscosity of the composition increases, and molding defects such as voids and wire flow occur during molding. On the other hand, when a phosphorus-based flame retardant such as red phosphorus or phosphoric acid ester is added to the epoxy resin composition, when the semiconductor device is exposed to high temperature and high humidity conditions, the phosphorus-based flame retardant is hydrolyzed to generate phosphoric acid. However, there is a big problem that this phosphoric acid corrodes aluminum wiring and reduces reliability.

[0006] In order to solve this problem, Japanese Patent No. 2843
No. 244 proposes an epoxy resin composition in which a compound obtained by coating the surface of red phosphorus with a coating layer made of a Si _X O _Y composition is used as a flame retardant, but the above moisture resistance reliability is improved. The current situation is that there are none. In addition, JP-A-1
No. 0-259292 discloses an epoxy resin composition which uses a cyclic phosphazene compound in an amount such that the amount of phosphorus atoms is 0.2 to 3.0% by weight based on the total amount of compounding ingredients excluding the filler. Although proposed, it is necessary to add a considerable amount to the epoxy resin composition in order to obtain flame retardancy,
In that case, there have been problems such as a decrease in curability and a decrease in electrical resistance in a high temperature environment.

[0007]

[Patent Document 1] Japanese Patent No. 2843244

[Patent Document 2] Japanese Patent Laid-Open No. 10-259292

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. It does not contain a bromide such as a brominated epoxy resin and an antimony compound such as antimony trioxide and is excellent in moldability and difficult. An object of the present invention is to provide a flame-retardant epoxy resin composition for semiconductor encapsulation, which is capable of obtaining a cured product having excellent flammability and moisture resistance reliability, and a semiconductor device encapsulated with the cured product of the resin composition.

[0009]

Means for Solving the Problems and Modes for Carrying Out the Invention The inventors of the present invention have made earnest studies to achieve the above object, and as a result, (A) epoxy resin, (B) curing agent, (C) inorganic substance Flame retardant for semiconductor encapsulation, which contains a filler and (D) a phosphazene compound having a melting point of 110 ° C. or higher and 130 ° C. or lower represented by the following average composition formula (1) as an essential component and substantially free of bromide and antimony compound. The epoxy resin composition is excellent in moldability, and a cured product having excellent flame retardancy and moisture resistance reliability can be obtained, and a semiconductor device sealed with the cured product of the epoxy resin composition is flame retardant. Further, they have found that they have excellent moisture resistance reliability, and have completed the present invention.

Therefore, according to the present invention, (A) epoxy resin (B) curing agent (C) inorganic filler (D) the melting point represented by the following average composition formula (1) is 110 ° C.
Above 130 ° C phosphazene compound

[Chemical 2] (In the formula, a, b, and n are 0 <a ≦ 0.05n, 1.90n
≦ b <2n, 2a + b = 2n, 3 ≦ n ≦ 6. ) Is an essential component and is substantially free of bromide and antimony compound, and is encapsulated with a flame-retardant epoxy resin composition for semiconductor encapsulation, and a cured product of this flame-retardant epoxy resin composition. A semiconductor device is provided.

Thus, the epoxy resin composition of the present invention is substantially free of bromide and antimony compound. Generally, in the epoxy resin composition, a brominated epoxy resin and antimony trioxide are blended in order to achieve flame retardancy. However, the epoxy resin composition of the present invention contains the brominated epoxy resin and trimonium trioxide. UL-94 and V-0 which are flame retardant standards can be achieved without using antimony oxide.

Here, as an alternative to the brominated epoxy resin or antimony trioxide, Al (OH) ₃ ,
Hydroxides such as Mg (OH) ₂ and phosphorus-based flame retardants such as red phosphorus and phosphoric acid esters are being studied. However, these known alternative flame retardants have a common drawback that the water resistance is weak, especially at high temperatures, and the flame retardant itself dissolves and decomposes to increase impurity ions in the extracted water. Therefore, when the semiconductor device sealed with the conventional flame-retardant epoxy resin composition substantially containing no bromide and antimony compound is left under high temperature and high humidity for a long time, aluminum wiring of the semiconductor device is corroded, There is a problem that the moisture resistance reliability is lowered.

As a result of intensive studies to solve the above-mentioned inconvenience, the present inventors have used a phosphazene compound having a melting point of 110 ° C. or higher and 130 ° C. or lower (D) represented by the average composition formula (1) as a flame retardant. As described above, the epoxy resin composition for semiconductor encapsulation does not increase the impurity ions in the extracted water as described above, and it is possible to obtain a cured product having excellent moldability, flame retardancy, and moisture resistance reliability. I found it. This phosphazene compound has high water resistance,
It has no effect of increasing impurity ions in the extracted water.

The present invention will be described in more detail below. As the epoxy resin (A) constituting the epoxy resin composition of the present invention, any epoxy resin having two or more epoxy groups in one molecule can be used and is not particularly limited. The epoxy resin, for example, novolac type epoxy resin, cresol novolac type epoxy resin, triphenol alkane type epoxy resin, aralkyl type epoxy resin, biphenyl skeleton-containing aralkyl type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, Heterocyclic epoxy resins, naphthalene ring-containing epoxy resins, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, stilbene type epoxy resins and the like can be mentioned, and one or more of them can be used in combination, No brominated epoxy resin is compounded in the present invention.

The above epoxy resin has a hydrolyzable chlorine content of 1,000 ppm or less, particularly 500 ppm or less,
It is preferable that the content of each of sodium and potassium is 10 ppm or less. Hydrolyzable chlorine is 100
Exceeding 0ppm, sodium or potassium 10p
If it exceeds pm, the moisture resistance may deteriorate if the semiconductor device is left under high temperature and high humidity for a long time.

The curing agent (B) used in the present invention is also not particularly limited. Among them, the curing agent is preferably a phenol resin, specifically, phenol novolac resin, naphthalene ring-containing phenol resin, aralkyl type phenol resin, triphenol alkane type phenol resin, biphenyl skeleton-containing aralkyl type phenol resin, biphenyl type phenol. Resin, alicyclic phenol resin, heterocyclic phenol resin, naphthalene ring-containing phenol resin, bisphenol A type resin, bisphenol F
Examples thereof include bisphenol type phenolic resins such as type resins, and of these, one kind or two or more kinds can be used in combination.

As with the epoxy resin, the curing agent preferably contains sodium and potassium in an amount of 10 ppm or less. 1 for sodium or potassium
If it exceeds 0 ppm, the humidity resistance may deteriorate when the semiconductor device is left under high temperature and high humidity for a long time.

Here, the compounding amount of the curing agent is not particularly limited, but is an effective curing amount of the epoxy resin, and particularly when a phenol resin is used as the curing agent, it is based on 1 mol of the epoxy group contained in the epoxy resin. The molar ratio of the phenolic hydroxyl group contained in the curing agent is preferably 0.5 to 1.5, more preferably 0.8 to 1.2.

Further, in the present invention, a curing accelerator is preferably used in order to accelerate the curing reaction between the epoxy resin and the curing agent. The curing accelerator is not particularly limited as long as it accelerates the curing reaction, and examples thereof include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenyl. Phosphorus compounds such as borane and tetraphenylphosphine / tetraphenylborate, triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine,
1,8-diazabicyclo (5.4.0) undecene-7
A tertiary amine compound such as 2-methylimidazole,
Imidazole compounds such as 2-phenylimidazole and 2-phenyl-4-methylimidazole can be used.

The compounding amount of the curing accelerator is an effective amount, but it is a curing accelerator for promoting the curing reaction between the epoxy resin such as the phosphorus compound, the tertiary amine compound and the imidazole compound and the curing agent (phenol resin). Is (A), (B),
The total amount of the component (D) is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight.

As the inorganic filler (C) blended in the epoxy resin composition of the present invention, those usually blended in the epoxy resin composition can be used. For example,
Examples thereof include fused silica and silicas such as crystalline silica, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, and glass fiber.

The average particle size and shape of these inorganic fillers are
Although not particularly limited, spherical fused silica having an average particle diameter of 5 to 30 μm is particularly preferable.

The filling amount of the inorganic filler is not particularly limited, but in order to enhance flame retardancy, it is preferable to fill the epoxy resin composition as much as possible within a range not impairing moldability. , (A), (B), and (D) with respect to 100 parts by weight in total, 200 to 1200 parts by weight,
Particularly, it is preferable to set it to 500 to 1000 parts by weight. Two
If it is less than 00 parts by weight, the expansion coefficient becomes large, and the stress applied to the semiconductor element increases, which may lead to deterioration of the element performance. On the other hand, if the amount exceeds 1200 parts by weight, the fluidity may be significantly reduced and the moldability may be deteriorated.

The inorganic filler is preferably pre-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to increase the bonding strength between the resin and the inorganic filler. . Examples of such coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and other epoxysilanes, N -Β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, aminosilane such as N-phenyl-γ-aminopropyltrimethoxysilane, silane cup such as mercaptosilane such as γ-mercaptosilane It is preferable to use a ring agent. The amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

The flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention uses (D) a phosphazene compound having a melting point of 110 ° C. or higher and 130 ° C. or lower, which is represented by the following average composition formula (1).

[Chemical 3] (In the formula, a, b, and n are 0 <a ≦ 0.05n, 1.90n
≦ b <2n, 2a + b = 2n, 3 ≦ n ≦ 6. )

Here, in the formula (1), n is 3 to 6, but preferably n = 3. In this case, in the present invention, the ratio of n = 3 is 90% by weight or more. Is preferred. The ratio of a, b, n is 0 <a ≦ 0.0.
5n, 1.90n ≦ b <2n, 2a + b = 2n.
When 0.05n <a, the intermolecular cross-linking of the phosphazene compound is large, so that the softening point becomes high and it is difficult to be compatible with the epoxy resin, and the expected flame retardant effect cannot be obtained. The ratio of a is preferably 0.005n ≦ a ≦ 0.05n, and the ratio of b is preferably 1.90n ≦ b ≦ 1.99n.

The phosphazene compound represented by the above formula (1) used in the present invention is preferably recrystallized once in order to remove impurities such as phosphoric acid and chlorine. By recrystallization, a compound with high crystallinity n = 3 can be selectively obtained, and as a result, the melting point also rises. Specifically, for example, a non-recrystallized phosphazene compound S
When the molecular weight distributions of PE-100 (manufactured by Otsuka Chemical Co., Ltd.) and the compound obtained by recrystallizing the same are observed by the peak area ratios of the GPC charts shown in FIGS. By recrystallizing 100, the ratio of n = 3 in the formula (1) was 72% by weight to 9%.
The melting point rises from 108 ° C to 114 ° C.

Further, since the amount of total phosphate ions extracted with hot water is also reduced by the recrystallization step, the flame-retardant epoxy for semiconductor encapsulation of the present invention to which the phosphazene compound represented by the above formula (1) is added. The resin composition is red phosphorus,
As compared with an epoxy resin composition containing a phosphorus-based flame retardant such as a phosphoric acid ester, a cured product having excellent hot water extraction characteristics and particularly excellent moisture resistance reliability can be obtained. The total phosphate ion can be measured by the following method.
That is, the epoxy resin composition is heated to 175 ° C., the molding pressure is 6.9 N / mm ² , and the molding time is 120 seconds.
A disc of 3 mm × 3 mm was formed, post-cured at 180 ° C. for 4 hours, and then pulverized with a Dista mill to 50 to 21.
10 g of particles having a particle size of 2 μm are collected. This powder is added to 50 ml of pure water and extracted at 125 ° C. for 20 hours. Next, the total phosphate ion concentration in the filtrate is measured by ICP emission spectrometry. The flame retardant epoxy resin composition for semiconductor encapsulation of the present invention has a total phosphate ion concentration measured under the above conditions of preferably 20 ppm or less, more preferably 10 ppm or less.

The phosphazene compound represented by the formula (1) can be recrystallized by a conventional method, and the phosphazene compound as the component (D) is dissolved as a solvent used for the recrystallization. There is no particular limitation as long as it is a combination of a rich solvent and a poor solvent that cannot be dissolved. Acetone and methyl isobutyl ketone (MIB
Examples thereof include ketones such as K), aromatic hydrocarbons such as benzene, toluene, and xylene, and examples of the poor solvent include aliphatic hydrocarbons such as hexane and alcohols such as methanol and ethanol. It is desirable that the solvent used for these recrystallizations has few impurities.

The addition amount of the phosphazene compound as the component (D) is 100% by weight of the total amount of the components (A), (B) and (D).
On the other hand, 1 to 50% by weight, particularly 2 to 20% by weight is preferable. If the addition amount is less than 1% by weight, a sufficient flame retardant effect may not be obtained, and if it exceeds 50% by weight, fluidity may be deteriorated.

In the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention, a molybdenum compound in which zinc molybdate is supported on an inorganic filler can be used as a flame retardant, and is represented by the above formula (1). By using a phosphazene compound and a molybdenum compound in which zinc molybdate is supported on an inorganic filler, a higher flame retardant effect can be obtained. Further, the addition amount of the component (D) can be minimized, and an effect as an ion trap agent can be expected.

As the inorganic filler for supporting zinc molybdate, silicas such as fused silica and crystalline silica,
Examples thereof include talc, alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, zinc oxide and glass fiber. In this case, the average particle size of the inorganic filler is preferably 0.1 to 40 μm, and particularly preferably 0.5 to 15 μm. The specific surface area is preferably 0.5~50m ² / g, it is particularly preferably 0.7~10m ² / g.

In the present invention, the average particle diameter can be obtained as, for example, a weight average value (or median diameter) by a laser light diffraction method or the like, and the specific surface area can be obtained by, for example, a BET adsorption method.

The content of zinc molybdate in the molybdenum compound in which zinc molybdate is supported on the inorganic filler is preferably 5 to 40% by weight, particularly 10 to 30% by weight. If the content of zinc molybdate is too low, a sufficient flame retardant effect may not be obtained, and if it is too high, the fluidity and curability during molding may be reduced.

As a molybdenum compound in which such a zinc molybdate is supported on an inorganic filler, for example, SHE
RWIN-WILLIAMS KEMGA D126
0,1261,911B, 911C etc. are mentioned.

The addition amount of the molybdenum compound in which zinc molybdate is supported on the inorganic filler is (A),
3 to 1 relative to 100 parts by weight of the total amount of the components (B) and (D).
00 parts by weight, especially 5 to 100 parts by weight are preferred. If it is less than 3 parts by weight, sufficient flame retardant effect may not be obtained, and if it exceeds 100 parts by weight, fluidity and curability may be deteriorated. In this case, the addition amount of zinc molybdate itself in the molybdenum compound is 0.1 to 40 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent,
In particular, 0.2 to 40 parts by weight is preferable. If it is less than 0.1 part by weight, a sufficient flame retardant effect may not be obtained,
If the amount is more than parts by weight, fluidity and curability may be deteriorated.

The flame-retardant epoxy resin composition for encapsulating a semiconductor of the present invention is another flame retardant, for example, a hydroxide such as aluminum hydroxide or magnesium hydroxide, within the range in which the purpose and effects of the present invention can be exhibited. Inorganic compounds such as zinc borate and zinc stannate, and silicone compounds can also be added. However, antimony compounds such as antimony trioxide are not mixed. Further, it is preferable not to add a phosphorus-based flame retardant other than phosphazene compounds such as red phosphorus and phosphoric acid ester.

If desired, various additives can be further added to the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention. For example, additives such as thermoplastic resins, thermoplastic elastomers, organic synthetic rubbers, low stress agents such as silicones, waxes such as carnauba wax, higher fatty acids and synthetic waxes, colorants such as carbon black, halogen trap agents, etc. It may be added and blended within a range that does not impair the object of the invention.

The flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention contains an epoxy resin, a curing agent, an inorganic filler, a phosphazene compound and other additives in a predetermined composition ratio, and the mixture is mixed with a mixer or the like. After sufficiently uniformly mixing, a melt mixing treatment with a heat roll, a kneader, an extruder, etc. is performed, followed by cooling and solidification, and pulverization to an appropriate size to obtain a molding material.

The thus obtained flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention can be effectively used for encapsulation of various semiconductor devices. In this case, the most general encapsulation method is used. A low-pressure transfer molding method can be mentioned as the above. The molding temperature of the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is 30 to 180 at 150 to 180 ° C.
Second curing is preferably performed at 150 to 180 ° C. for 2 to 16 hours.

[0041]

INDUSTRIAL APPLICABILITY The flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is excellent in moldability, and at the same time, a cured product having excellent flame retardancy and moisture resistance reliability can be obtained. Moreover, since the epoxy resin composition does not contain a bromide such as a brominated epoxy resin or an antimony compound such as antimony trioxide, there is no adverse effect on the human body or the environment. Further, the semiconductor device encapsulated with the cured product of the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is excellent in flame retardancy and moisture resistance reliability, and is particularly useful from an industrial point of view. is there.

[0042]

EXAMPLES The present invention will be specifically shown below by showing examples of preparation of phosphazene compounds and examples and comparative examples of epoxy resin compositions, but the present invention is not limited to the following examples. In the following examples,% means% by weight.

[Preparation Example A] A phosphazene compound having a melting point of 108 ° C. represented by the following average composition formula (2) (manufactured by Otsuka Chemical Co., Ltd .; SPE-100, phosphorus atom content 11.0%, sulfur) under nitrogen atmosphere. 100 g of atomic content 0.14%) was dissolved in 225 g of toluene. Hexane was gradually added when a uniform solution was obtained, the dropping was completed before the solution became cloudy, and the mixture was left standing in a refrigerator. After the crystals were separated by filtration, they were washed with a mixed solvent of toluene / hexane, extracted by a liquid separation operation and then dried under reduced pressure to give white crystals (melting point: 11
50 g of a phosphazene compound (4 ° C.) was obtained. As a result of fluorescent X-ray analysis, the phosphorus atom content of this compound was 11.6%,
The sulfur atom content was 0.13%.

[Chemical 4] (In the formula, a, b, and n ′ are 0 <a ≦ 0.05n ′, 1.9.
0n ′ ≦ b <2n ′, 2a + b = 2n ′, 3 ≦ n ′ ≦ 1
Is a number that satisfies 000. )

The phosphazene compound (SPE-10
0) and the compound after recrystallization (compound obtained in Preparation Example A) after GPC and DSC measurement results are shown in FIGS.
Shown in.

[Examples 1 to 4 and Comparative Examples 1 to 5] The components shown in Table 1 were uniformly melt-mixed with a hot double roll, cooled and pulverized to obtain an epoxy resin composition for semiconductor encapsulation. . The following properties (i) to (vii) of these compositions were measured. The results are shown in Table 2. (I) Spiral flow value Using a mold conforming to the EMMI standard, temperature 175 ° C,
The measurement was performed under the conditions of a molding pressure of 6.9 N / mm ² and a molding time of 120 seconds. (Ii) Gelation time The gelation time of the composition was measured on a hot plate at 175 ° C. (Iii) Molding hardness According to JIS-K6911, the temperature is 175 ° C., the molding pressure is 6.9 N / mm ² , and the molding time is 90 × 10 × 4 ×.
The hardness at the time of molding a 100 mm rod was measured with a Barcol hardness meter. (Iv) Extraction water phosphate ion temperature 175 ° C., molding pressure 6.9 N / mm ² , molding time 1
Form a disk of 50φ x 3 mm under the condition of 20 seconds and 180
Post cure at 4 ° C for 4 hours. Then, it grind | pulverized with the Dista mill, and 10g of 50-212 micrometers particle size was extract | collected. Add this powder to 50 ml of pure water,
Extracted for 20 hours. The total phosphate ion concentration in the filtrate was measured by ICP emission spectrometry. (V) Flame retardancy Based on the UL-94 standard, the flame retardancy of a 1/16 inch thick plate was examined. (Vi) A 6 × 6 mm size silicon chip on which moisture-resistant aluminum wiring is formed is bonded to a 14-pin-DIP frame (42 alloy), and the aluminum electrode on the chip surface and the lead frame are wire-bonded with a gold wire of 30 μmφ. After that, the epoxy resin composition is added thereto at a temperature of 175 ° C.,
Molding was carried out under conditions of molding pressure of 6.9 N / mm ² and molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. After each of these 20 packages was left for 500 hours in a 140 ° C./85% RH atmosphere with a DC bias voltage of −5 V, the number of packages in which aluminum corrosion occurred was examined. (Vii) High temperature storage reliability A 6 × 6 mm size silicon chip with aluminum wiring is bonded to a 14 pin-DIP frame (42 alloy), and the aluminum electrode on the chip surface and the lead frame are connected with a 30 μmφ gold wire. After wire bonding, the epoxy resin composition is applied thereto at a temperature of 175 ° C.,
Molding was carried out under conditions of molding pressure of 6.9 N / mm ² and molding time of 120 seconds, and post-cured at 180 ° C. for 4 hours. After leaving 20 of each of these packages in an atmosphere of 200 ° C. for 500 hours, they were dissolved in fuming nitric acid and opened, and the tensile strength of the gold wire was measured. When the tensile strength was 70% or less of the initial value, it was regarded as a defect, and the number of defects was examined.

[0046]

[Table 1]

Epoxy resin: o-cresol novolac type epoxy resin, EOCN1020-55 (Nippon Kayaku, epoxy equivalent 200) Curing agent: phenol novolac resin, DL-92 (Meiwa Kasei, phenolic hydroxyl equivalent 110) Molybdenum compound : Zinc molybdate, KEMGARD
911C (manufactured by SHERWIN-WILLIAMS, content of zinc molybdate 18% by weight, core material: talc, average particle size 2.0 μm, specific surface area 2.0 m ² / g) Inorganic filler: spherical fused silica (manufactured by Tatsumori, average) Particle size 20
μm) Curing catalyst: DBU (manufactured by San Apollo) Release agent: Carnauba wax (manufactured by Nikko Fine Products) Carbon black: Denka Black (manufactured by Denki Kagaku) Silane coupling agent: KBM-403, γ-glycidoxypropyltrimethoxy Silane (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0048]

[Table 2]

As is clear from the results shown in Table 2, the flame-retardant epoxy resin composition for semiconductor encapsulation of the present invention is excellent in curability, flame retardancy, moisture resistance reliability, and high temperature electrical resistance characteristics. An excellent cured product can be obtained, and the semiconductor device sealed with the cured product of the epoxy resin composition of the present invention has excellent flame retardancy and moisture resistance reliability. Moreover, since the resin composition does not contain a bromide such as a Br-epoxy resin or an antimony compound such as antimony trioxide, there is no adverse effect on the human body or the environment.

[Brief description of drawings]

FIG. 1 GP of phosphazene compound (SPE-100)
It is a C chart.

FIG. 2 is a GPC chart after recrystallization of a phosphazene compound (SPE-100).

FIG. 3 DS of phosphazene compound (SPE-100)
It is a C chart.

FIG. 4 is a DSC chart after recrystallization of a phosphazene compound (SPE-100).

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI Theme Coat (reference) H01L 23/29 H01L 23/30 R 23/31 (72) Inventor Shoichi Nagata Matsuida Town, Usui District, Gunma Prefecture Hitomi No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Hiroyuki Takenaka Osamu Matsuida Town, Usui District, Gunma Prefecture Hitomi No. 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Invention Person Shingo Ando 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Kazutoshi Tokichi 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. (72) Inventor, Toshio Shiobara, Matsuida Town, Usui District, Gunma Prefecture Hitomi No. 1 10 Shin-Etsu Chemical Co., Ltd. Silicon Electron Materials Technology Laboratory F-term (reference) 4H017 AA04 AA24 AA27 AA29 AA31 AB08 AC16 AD06 AE05 4H028 AA08 AA38 AA40 AA42 BA06 4J002 CC03X CC06X CC27X CD001 CD021 CD031 CD041 CD051 DE061 CD051 DE051 CD06 DE1 DE189 DF017 DJ007 DJ017 DK007 DL007 EW158 FA047 FB299 FD017 FD14X FD146 GJ02 GQ05 4M109 AA01 CA21 EB07 EB12

Claims (6)

[Claims] 1. (A) Epoxy resin (B) Curing agent (C) Inorganic filler (D) Melting point represented by the following average composition formula (1) is 110 ° C.
Phosphazene compound above 130 ° C. (In the formula, a, b, and n are 0 <a ≦ 0.05n, 1.90n
≦ b <2n, 2a + b = 2n, 3 ≦ n ≦ 6. ) Are essential components, and a bromide and an antimony compound are not substantially contained, The flame-retardant epoxy resin composition for semiconductor encapsulation. 2. The flame-retardant material for semiconductor encapsulation according to claim 1, wherein (D) the phosphazene compound represented by the average composition formula (1) has a ratio of n = 3 of 90% by weight or more. Epoxy resin composition. 3. The flame-retardant epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the phosphazene compound (D) represented by the average composition formula (1) is obtained by recrystallization. object. 4. The flame-retardant epoxy resin composition for semiconductor encapsulation according to claim 1, further comprising a molybdenum compound in which zinc molybdate is supported on an inorganic filler. 5. The phosphate ion concentration in the extracted water obtained by hot water extraction of the flame-retardant epoxy resin composition is 20 ppm.
It is the following, The flame-retardant epoxy resin composition for semiconductor encapsulation according to any one of claims 1 to 4. 6. A semiconductor device encapsulated with the cured product of the flame-retardant epoxy resin composition according to claim 1. Description: