JP2002371194A - Resin composition for sealing and semiconductor-sealed device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a halogen and antimony oxide-free resin composition for sealing excellent in flame resistance, continuous productivity and moisture resistance, and to provide a semiconductor-sealed device. SOLUTION: This resin composition for sealing includes (A) 60 to 90 wt.% based on the total resin composition, of an inorganic filler having maximum particle diameter <=200 μm and average particle diameter 1 to 60 μm, (B) a thermosetting resin, (C) a hardening agent, (D) 0.1 to 10 wt.% of a phosphazene compound and (E) 0.1 to 2 wt.% of a zirconium based ion exchanging material as the essential components. And the semiconductor-sealed device obtained by sealing a semiconductor tip with a hardened product of the resin composition for sealing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a halogen (chlorine,
The present invention relates to a sealing resin composition having excellent flame retardancy without adding a bromine-based flame retardant compound and an antimony compound, and having excellent moldability, moisture resistance and reliability, and a semiconductor sealing device.

[0002]

2. Description of the Related Art In a semiconductor device, a sealing resin is generally provided with flame retardancy, and a halogen (chlorine, bromine) flame retardant compound and an antimony compound are used alone or in combination as a flame retardant formulation. This shows the flame retardant effect. Specifically, a combination of a brominated epoxy resin and antimony trioxide is generally used. However, halogen (chlorine, bromine) based flame retardant compounds added to exhibit the flame retardant effect of the encapsulating resin composition, particularly brominated epoxy resins and antimony compounds added to assist the flame retardant effect thereof In particular, antimony trioxide has a disadvantage that the reliability of the semiconductor device is reduced. Not only that, but it has recently been pointed out that it has a negative impact on the environment.

[0003] For this reason, there has been a strong demand for the development of a sealing resin composition which does not contain a halogen (chlorine, bromine) flame retardant compound and an antimony compound and has excellent moldability, moisture resistance and reliability. Therefore, studies on phosphate ester-based flame retardants, metal hydrates, and the like as alternative materials have been widely promoted. However, in the case of a phosphate ester-based flame retardant, even if the flame retardant effect is obtained, phosphoric acid generated by hydrolysis causes a decrease in the moisture resistance reliability of the semiconductor encapsulation device, and sufficient reliability is obtained. Can not secure. Also,
Metal hydrates also have drawbacks in that not only sufficient formability cannot be ensured, but also that the deterioration of the moisture absorption properties greatly reduces the reliability of the semiconductor device. For this reason, there has been a strong demand for the development of a sealing resin composition which is excellent in moldability, moisture resistance and reliability and does not contain a halogen (chlorine, bromine) flame retardant compound and antimony oxide.

[0004] The phosphazene compound used in the present invention also has good hydrolysis characteristics as compared with the phosphate ester-based flame retardant, but has better hydrolysis characteristics than halogen (chlorine, bromine) -based flame retardant compounds and antimony compounds. In this case, ionic impurities due to hydrolysis tend to increase.
Furthermore, currently commonly used ion exchangers use antimony in the nucleus.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks and to meet the above-mentioned demands. The present invention provides a novel flame retardant compound containing no halogen (chlorine, bromine) flame retardant compound and antimony oxide. A resin composition for encapsulation and a semiconductor having good moldability, moisture resistance and reliability while imparting sufficient flame retardancy by blending an appropriate combination of a phosphorus-nitrogen flame retardant and a zirconium ion exchanger. It is intended to provide a sealing device.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result,
By using a phosphazene compound as a flame retardant and removing ionic impurities using a zirconium-based ion exchanger, sufficient flame retardancy, moldability, moisture resistance and reliability are improved, and the above object is achieved. And completed the present invention.

That is, according to the present invention, (A) the maximum particle diameter is 20
0 [mu] m or less, an inorganic filler having an average particle diameter of 1 [mu] m to 60 [mu] m, (B) a thermosetting resin, (C) a curing agent,
The (D) phosphazene compound and the (E) zirconium-based ion exchanger are essential components, and the (A) inorganic filler is 60 to 90% by weight, and the (D) phosphazene compound is 0.1% by weight based on the entire resin composition. 1 to 10% by weight, and 0.1 to 2% of the (E) zirconium ion exchanger.
It is a resin composition for encapsulation characterized by containing each in a proportion of% by weight. The semiconductor sealing device is characterized in that the semiconductor chip is sealed with a cured product of the sealing resin composition in which the thermosetting resin (B) is an epoxy resin.

Hereinafter, the present invention will be described in detail.

The inorganic filler (A) used in the present invention includes silica powder, alumina, aluminum nitride, silicon nitride, talc, calcium carbonate, titanium oxide, glass fiber, and the like. These can be mixed and used. Of these, fusible silica powder, crystalline silica powder, and powders of alumina, silicon nitride, and aluminum nitride are particularly preferable, and these are often used. The sealing resin composition has a maximum particle diameter of 200 μm or less and an average particle diameter of 1 μm or more and 60 μm or less.
It is necessary to be less than μm. The inorganic filler is desirably contained in a proportion of 60 to 90% by weight based on the entire resin composition. If the proportion is less than 60% by weight, heat resistance, moisture resistance, soldering heat resistance, mechanical properties and moldability deteriorate, and if it exceeds 90% by weight, the bulk becomes large and the moldability deteriorates, which is not suitable for practical use. .

The (B) thermosetting resin used in the present invention includes, for example, urea resin, melamine resin, phenol resin, resorcinol resin, epoxy resin, polyurethane resin, vinyl acetate resin, polyvinyl alcohol resin, acrylic resin, vinyl urethane Resin, silicone resin, α
-Olefin maleic anhydride resin, polyamide resin, polyimide resin and the like, and these can be used alone or in combination of two or more. Among them, epoxy resin can be used industrially advantageously.

The (C) curing agent used in the present invention includes:
As long as the curing agent for the (B) thermosetting resin is generally used, it can be used. However, when the (B) thermosetting resin is an epoxy resin, the curing agents such as amines and phenol Resin or imidazole alone or 2
More than one kind can be mixed and used.

The phosphazene compound (D) of the flame retardant used in the present invention is represented by the following structural formula.

[0013]

Embedded image (Where R ¹ and R ^{2 each} represent an organic group such as an alkoxy group, a phenoxy group, an amino group, an allyl group, and n represents 1
Indicates an integer greater than or equal to)

Embedded image (Where R ¹ and R ^{2 each} represent an organic group such as an alkoxy group, a phenoxy group, an amino group, or an allyl group;
These phosphazene compounds can be used alone or in combination of two or more. Specific compounds include, for example,

Embedded image (Where n represents an integer of 3 to 6).

The phosphazene compound is preferably contained in an amount of 0.1 to 10% by weight based on the whole resin composition. If this proportion is less than 0.1% by weight, the effect of flame retardancy cannot be sufficiently obtained, and if it exceeds 10% by weight, it oozes on the surface of the cured product of the sealing resin and adversely affects the properties of the cured product. Is not suitable for practical use and is not preferred.

The (E) zirconium-based ion exchanger used in the present invention is an inorganic ion exchanger containing zirconium as a main component. Specific examples include a zirconium-based ion exchanger IXE-800 (trade name, manufactured by Toagosei Co., Ltd.). (E) The zirconium-based ion exchanger is desirably contained in an amount of 0.1 to 2% by weight based on the entire resin composition. If the proportion is less than 0.1% by weight, the ion-trapping effect cannot be sufficiently obtained, and if it exceeds 2% by weight, the ion-trapping effect is not improved, so the above content is appropriate.

The sealing resin composition of the present invention comprises the above-mentioned inorganic filler, thermosetting resin, phosphazene compound, curing agent and zirconium-based ion exchanger as main components.
To the extent not inconsistent with the object of the present invention, and if necessary, for example, natural waxes, synthetic waxes, straight-chain aliphatic metal salts, acid amides, esters, paraffin-based release agents, elastomers , A colorant such as carbon black, a treating agent for an inorganic filler such as a silane coupling agent, various curing accelerators, and the like can be appropriately added and blended.

A general method for preparing the encapsulating resin composition of the present invention as a molding material includes the above-mentioned inorganic filler, thermosetting resin, phosphazene compound, curing agent,
After mixing the zirconium-based ion exchanger and other components and mixing them sufficiently uniformly using a mixer, etc., they are further subjected to a melt mixing process using a hot roll, or a mixing process using a kneader, etc., then cooled and solidified, and pulverized to an appropriate size. To form a molding material. When the molding material thus obtained is applied to sealing, coating, insulating, etc. of electronic parts or electric parts including semiconductor sealing, excellent properties and reliability can be imparted.

The semiconductor device of the present invention can be easily manufactured by sealing a semiconductor chip using the sealing resin obtained as described above. The most common method of sealing is a low pressure transfer molding method, but sealing by injection molding, compression molding, casting or the like is also possible. The sealing resin composition is heated and cured at the time of sealing, and finally a semiconductor sealing device sealed with a cured product of this composition is obtained. Curing by heating is 15
Desirably, the composition is cured by heating to 0 ° C. or higher. The semiconductor device for sealing is not particularly limited to, for example, an integrated circuit, a large-scale integrated circuit, a transistor, a thyristor, a diode, and the like.

[0019]

The sealing resin composition and the semiconductor encapsulating apparatus of the present invention can obtain desired properties by using a phosphazene compound and a zirconium-based ion exchanger as the compounding components. That is, by combining a predetermined amount of a phosphazene compound and a zirconium-based ion exchanger, while maintaining sufficient moldability, imparts excellent flame retardancy of the resin composition, and in a semiconductor device from the stability of the compound. Moisture resistance and reliability can be improved.

[0020]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, “%” means “% by weight”.

Example 1 Cresol novolak type epoxy resin (epoxy equivalent 2
11), 5% of a novolak type phenol resin (phenol equivalent: 105) and IXE-800 (trade name, manufactured by Toa Gosei Chemical Industry Co., Ltd.) of a zirconium-based ion exchanger.
1. 5%, phosphazene compound of formula 3 (melting point: 100 ° C.)
5%, fused silica powder MSR-2212 (Tatsumori Co., trade name) 80%, curing catalyst PP-200 (Hokuko Chemical Co., trade name) 0.2%, ester wax Carnava No. 1 (Nikko) Fine Chemical Co., trade name) and coupling agent Y-9669 (Nihon Yunika Co., Ltd. trade name)
0.8%, mix at room temperature, further 90-95 ° C
And cooled and pulverized to produce a molding material.

This molding material is transfer-injected into a mold heated to 175 ° C. and cured to form a molded product (sealed product).
Was molded. Its continuous productivity was very good. In addition, the molded article was subjected to a test for flammability and moisture resistance. Table 1 shows the results.

Example 2 Cresol novolak type epoxy resin (epoxy equivalent 2
00) 9%, 7% of novolak type phenol aralkyl resin (phenol equivalent: 175), 0.5% of IXE-800 zirconium-based ion exchanger (trade name, manufactured by Toa Gosei Chemical Industry Co., Ltd.), Melting point 100
C) 2.5%, fused silica powder MSR-2212 (Tatsumori Co., trade name) 80%, curing catalyst PP-200 (Hokuko Chemical Co., trade name) 0.2%, ester wax carnauba No. 1 (trade name, manufactured by Nikko Fine Chemical Co., Ltd.) and 0.8% of coupling agent Y-9669 (trade name, manufactured by Nippon Yunika Co., Ltd.) were blended and mixed at room temperature.
The mixture was kneaded at 5 ° C and cooled and pulverized to produce a molding material.

With this molding material, a molded product was obtained in the same manner as in Example 1. Its continuous productivity was very good. In addition, the molded article was subjected to a test for flammability and moisture resistance. Table 1 shows the results.

Example 3 Biphenyl type epoxy resin (epoxy equivalent: 193) 7%
Novolak type phenol resin (phenol equivalent 10
5) 3% IXE-80 zirconium ion exchanger
0 (manufactured by Toa Gosei Chemical Industry Co., Ltd.) 0.3%, phosphazene compound of formula 3 (melting point 100 ° C.) 0.7%, MSR-2212 (manufactured by Tatsumori Co., Ltd., trade name) as fused silica powder
88%, curing catalyst PP-200 (Hokuko Chemical Co., Ltd., 0.15%), ester wax Carnava No. 1 (Nikko Fine Chemical Co., Ltd., trade name) and coupling agent Y-9669 (Nihon Yunika Co., Ltd.) Made, trade name) 0.8
5% was blended, mixed at room temperature, further kneaded at 90 to 95 ° C., and cooled and pulverized to produce a molding material.

With this molding material, a molded product was obtained in the same manner as in Example 1. Its continuous productivity was very good. In addition, the molded article was subjected to a test for flammability and moisture resistance. Table 1 shows the results.

Comparative Example 1 ESCN-19 of cresol novolac type epoxy resin
5XL (manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 200) 11
%, AER-8028 brominated epoxy resin (trade name, epoxy equivalent: 370, manufactured by Asahi Chiba Co., Ltd.) 1.5%, BRG of novolac type phenol resin (phenol equivalent: 105, manufactured by Showa Polymer Co., Ltd.) 5.5%, MS as fused silica powder
R-2212 (trade name, manufactured by Tatsumori) 78%, antimony trioxide PATOX-MZ (trade name, manufactured by Nippon Seiko) 2
%, Curing catalyst PP-200 (Hokuko Chemical Co., Ltd., trade name)
0.2%, ester wax Carnava No. 1 (trade name, manufactured by Nikko Fine Chemical Co., Ltd.) and coupling agent Y
0.8% of -9669 (trade name, manufactured by Nippon Yunika Co., Ltd.) was mixed, mixed at room temperature, further kneaded at 90 to 95 ° C., and cooled and pulverized to prepare a molding material.

With respect to this molding material, a molded product was obtained and various tests were performed in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 2 ESCN-19 of cresol novolac type epoxy resin
5XL (manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 200) 11
%, BRG of a novolak type phenol resin (phenol equivalent: 105, manufactured by Showa Polymer Co., Ltd.) 5%, phosphazene compound of Chemical Formula 3 (melting point 100 ° C.) 2.5%, MSR-2212 (manufactured by Tatsumori Co. , Product name) 80%,
Curing catalyst PP-200 (trade name, manufactured by Hokuko Chemical Co., Ltd.)
2%, ester wax Carnava No. 1 (trade name, manufactured by Nikko Fine Chemical Co., Ltd.) and coupling agent Y-9
669 (manufactured by Nihon Yunika Co., Ltd.) 0.8%
The mixture was mixed at room temperature, further kneaded at 90 to 95 ° C, and cooled and pulverized to prepare a molding material.

With respect to this molding material, a molded product was obtained and various tests were performed in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 3 ESCN-19 of cresol novolac type epoxy resin
5XL (manufactured by Sumitomo Chemical Co., Ltd., epoxy equivalent: 200) 11
%, A novolak type phenol resin (phenol equivalent 1
05) 5%, IXE-8 of zirconium-based ion exchanger
00 (trade name, manufactured by Toa Gosei Chemical Industry Co., Ltd.) 0.5%, phosphate-based flame retardant PX-200 (trade name, manufactured by Hokuko Chemical Co., Ltd.) 2.5%, MSR-2212 as fused silica powder
80%, PP-200 curing catalyst
(Hokuko Chemical Co., Ltd., trade name) 0.2%, ester wax Carnava No. 1 (Nikko Fine Chemical Co., trade name) and coupling agent Y-9669 (Nihon Unica Co., trade name) 0.8% Was mixed at room temperature, kneaded at 90 to 95 ° C., and cooled and pulverized to produce a molding material.

With respect to this molding material, a molded product was obtained and various tests were performed in the same manner as in Example 1. Table 2 shows the results.

[0033]

[Table 1] 1: 120 × 12 × 0.8 by transfer molding
mm, and left at 175 ° C for 8 hours.
A flammability test was performed based on the UL-94V flame resistance test standard.

* 2: A silicon chip (test element) having two aluminum wirings was bonded to a copper frame using a molding material, and transfer-molded at 175 ° C. for 2 minutes.
After making TO-92 molded product, post-curing at 175 ° C for 4 hours, solder immersion at 260 ° C, 127 ° C,
PCT was performed in 2.5 atm of saturated steam, and the disconnection due to aluminum corrosion was evaluated as defective.

[0035]

[Table 2] 1: 120 × 12 × 0.8 by transfer molding
mm, and left at 175 ° C for 8 hours.
A flammability test was performed based on the UL-94V flame resistance test standard.

* 2: A silicon chip (test element) having two aluminum wirings was adhered to a copper frame using a molding material, and transfer molded at 175 ° C. for 2 minutes.
After making TO-92 molded product, post-curing at 175 ° C for 4 hours, solder immersion at 260 ° C, 127 ° C,
PCT was performed in 2.5 atm of saturated steam, and the disconnection due to aluminum corrosion was evaluated as defective.

[0037]

As is clear from the above description and Tables 1 and 2, the encapsulating resin composition and the semiconductor encapsulating apparatus of the present invention have excellent flame retardancy but are continuously produced. It was excellent in moisture resistance reliability without lowering the characteristics, and as a result, disconnection failures and the like due to electrode corrosion could be significantly reduced, and long-term reliability could be guaranteed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 63/00 C08L 63/00 C H01L 23/29 H01L 23/30 R 23/31 F-term (Reference) 4J002 AA02W BE02W BF02W BG00W BH00W CC03W CC03X CC16W CC18W CD00W CK02W CL00W CM04W CP03W DB019 DE138 DE148 DE238 DF018 DJ018 DJ048 DL008 EN006 EU116 EW157 FA048 FD018 FD137 FD14FD FD146 GQ01 FA07A01FAQA DCA EB18 EC01

Claims (3)

[Claims] (A) the maximum particle diameter is 200 μm or less,
A resin composition comprising, as essential components, an inorganic filler having an average particle size of 1 μm or more and 60 μm or less, (B) a thermosetting resin, (C) a curing agent, (D) a phosphazene compound, and (E) a zirconium-based ion exchanger. (A)
The inorganic filler is 60 to 90% by weight, the (D) phosphazene compound is 0.1 to 10% by weight, and the (E) zirconium-based ion exchanger is 0.1 to 2% by weight.
A resin composition for sealing characterized by containing each. 2. The sealing resin composition according to claim 1, wherein (A) the inorganic filler is any one of a group of silica, silicon nitride, alumina and aluminum nitride or a mixture of two or more thereof. 3. A semiconductor characterized in that a semiconductor chip is sealed with a cured product of the sealing resin composition according to claim 1, wherein (B) the thermosetting resin is an epoxy resin. Sealing device.