JPH0415252A - Resin composition for semiconductor sealing - Google Patents

Abstract

PURPOSE:To obtain a resin composition for semiconductor sealing having sufficient soldering-heat resistance, high flow and excellent cracking resistance and reliability of humidity resistance by mixing a specified polyether copolymer with an inorganic filler. CONSTITUTION:A resin composition prepared by mixing a polyether copolymer comprising repeating units of formula I and repeating units of formula II and having a content of repeating units of formula I {in terms of a molar ratio : (I)/[(I)+(II)]} of 0.15-0.4 and a melt viscosity of below 1000P at 400 deg.C and a shear rate of 1000sec<1> with 10-80wt.%, based on the polyether copolymer inorganic filler. When the compositional ratio of the repeating units of formula I is below 0.15, the glass transition temperature of the polyether copolymer is lowered and the heat resistance is lowered, or the melting point is increased and the moldability is worsened. When it is above 0.4, the crystallinity of the polyether copolymer is lost and the heat resistance and solvent resistance are worsened.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel resin composition for semiconductor encapsulation, and more specifically, for semiconductor encapsulation that can be suitably used in the electric and electronic fields. The present invention relates to a resin composition for use.

[Prior art and the problem to be solved by the invention] Conventionally,
To shield semiconductor elements from external dust, moisture, etc.
Various sealants are used.

Typical sealants include ceramics and resins, but resins are the mainstream because of their price. Further, as the numerical resin sealant, a thermosetting sealant is used.

However, thermosetting resins, which are often used as encapsulating materials for semiconductor devices such as transistors and ICs, have various problems such as long molding times, long post-curing times, and poor yields. There are some problems.

In addition, in recent years, there have been cases where sealing is done with PP5 (polyphenylene sulfite) resin, which has problems such as cracking and poor moisture resistance.

The present invention has been made based on the above circumstances.

The object of the present invention is to have sufficient soldering heat resistance by using a resin composition containing a polyether copolymer and a specific amount of inorganic filler as a semiconductor encapsulating material.
It is an object of the present invention to provide a resin composition for semiconductor encapsulation that has high fluidity and excellent crack resistance and moisture resistance and reliability.

[Means for Solving the Problems] The configuration of the present invention to achieve the above object is as follows:
) N (I) and the repeating unit represented by the following formula (■): (■) The content ratio of the repeating unit represented by the formula (I) [cell ratio.

(I)/((I)+(II))] from 0.15 to 0.
4, temperature 400°C, shear rate 1,000
A semiconductor characterized by blending an inorganic filler with a polyether copolymer having a melt viscosity at sec-1 of less than 1.000 voids at a content of 10 to 80% by weight. This is a sealing resin composition.

This will be explained in detail below.

One of the important points in the polyether copolymer used in the present invention is that the polyether copolymer has a repeating unit represented by the formula (1) and the formula (1). (II
), and the content or molar ratio of the repeating units represented by formula (1) is in the range of 0.15 to 0.4.

The composition ratio of the repeating unit represented by the formula (I) is 0.
If it is less than 15, the glass transition temperature of the polyether copolymer will be low, resulting in a decrease in heat resistance, or the melting point will be high, leading to deterioration in moldability. On the other hand, if it exceeds 0.4, the polyether copolymer will lose its crystallinity and its heat resistance and solvent resistance will decrease.

Furthermore, in the polyether copolymer used in the present invention, it is important that the melt viscosity at a temperature of 400° C. and a shear rate of 1,000 mm is less than 1.000 voids.

If the melt viscosity exceeds 1.000 voids, there is a risk of disconnection in the IC circuit, for example, during molding of the sealant.

The polyether copolymer used in the present invention has high fluidity and heat resistance sufficient to withstand the melting temperature of solder. It is suitable as a base resin for stoppers.

This polyether copolymer can be produced as follows.

1. Method for producing a polyether copolymer - A polyether copolymer is produced by reacting dihalogenobenzonitrile, 4,4'-biphenol, and an alkali metal compound in the presence of a neutral polar solvent in a specific usage ratio. After that, the reaction product can be produced by carrying out a copolymerization reaction with a specific amount of 4.4°-dihalogenobenzophenone.

Specific examples of the dihalogenobenzonitrile that can be used include 2,6-dihalogenobenzonitrile represented by the following formula: (wherein, X is a halogen atom); Examples include 2,4-dihalogenobenzonitrile represented by the following formula: (wherein, X has the same meaning as above).

Among these, preferred are 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, and 2.4-dichlorobenzonitrile.
2.6-dichlorobenzonitrile is particularly preferred.

The dihalogenobenzonitrile and 4 represented by the following formula;
, 4°-biphenol in the presence of an alkali metal compound and a neutral polar solvent.

The alkali metal compound to be used is
Any substance that can convert °-biphenol into an alkali metal salt may be used, and there are no particular limitations, and preferred are alkali metal carbonates and alkali metal hydrogen carbonates.

Examples of the alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, rhodium carbonate,
Examples include cesium carbonate.

Among these, preferred are sodium carbonate and potassium carbonate.

Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
Examples include rubidium hydrogen carbonate and cesium hydrogen carbonate.

Among these, sodium carbonate and potassium hydrogen carbonate are preferred, and among the various alkali metal compounds mentioned above, sodium carbonate and potassium carbonate are particularly preferred.

Examples of the neutral polar solvent include N,N dimethylformamide, N,N-diethylformamide, N,N-
Dimethylacetamide, N.

N-diethylacetamide, N,N-sibropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-
Isopropyl-2-pyrrolidone, N-isobutyl-2-
Pyrrolidone, N-n-propyl-2-pyrrolidone, N-
n-butyl-2-pyrrolidone, N-cyclohexyl 2-
pyrrolidone, N-methyl-3-methyl-2-pyrrolidone,
N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-doberitone, N
-isopropyl-2-piperitone, N-methyl-6-methyl-2-piperitone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide,
1-Methyl-1-oxosulfolane l-ethyl-1-
Examples include oxosulfolane, l-phenyl-1-oxosulfolane, dimethylimitazolicinone, and diphenylsulfone.

An example of a method for producing a polyether copolymer is to react the dihalogenobenzonitrile with the 4,4-phenol in the presence of the alkali metal compound 5i@ and the neutral polar solvent. The reaction product obtained in this manner is reacted with the 4,4''-dihalogenobenzophenone.

The 4,4'-dihalogenobenzophenone used is a compound represented by the following formula (where X has the same meaning as above), and in the method of the present invention, 4. 4'-
Difluorobenzophenone and 4,4'-dichlorobenzophenone can be particularly preferably used.

The molar ratio of the dihalogenobenzonitrile, the 4,4'-biphenol, and the alkali metal compound to the 4,4'-biphenol is usually 0.15 to 0. The ratio of the alkali metal compound is usually 1.03 to 2.5G, preferably 1.05 to 1.25.

Is there any particular restriction on the amount of the neutral polar solvent used? Usually, the amount of the dihalogenobenzonitrile and the 4.
The amount is selected in the range of 200 to 2.000 parts by weight per 100 parts by weight of the 4'-biphenol and the alkali metal compound.

To obtain a polyether copolymer, for example, the dihalogenobenzonitrile and the 4.4° to biphenol are mixed in the neutral polar solvent.

Adding the alkali metal compound at the same time to Rrl
After the dihalogenobenzonitrile and the 4,4'biphenol are reacted, the 4.4°-dihalogenobenzophenone is further added, usually to a concentration of 150 to 38
The series of reactions is carried out at a temperature of 0°C, preferably in the range of 180 to 30'C. If the reaction temperature is less than 150°C, the reaction rate is too slow to be practical. 38
If the temperature exceeds 0°C, side reactions may occur.

In addition, the reaction time of this series of reactions is usually 0.1 to 1
0 hours, preferably 1 hour to 5 hours.

After completion of the reaction, the polyether copolymer is separated and purified from the resulting neutral polar solvent solution containing the polyether copolymer according to a known method to obtain a polyether copolymer. Something comes up.

In addition, the polyether copolymer used in the present invention is
It can also be obtained by simultaneously adding dihalogenobenzonitrile, biphenol, alkali metal salt, and dihalogenobenzophenone to a neutral polar solvent solution.

The obtained polyether copolymer had a melt viscosity of 1.0 at a temperature of 400°C and a shear rate of 1,00 Qilj-'.
It has a crystal melting point of 320-400.
It is ℃.

1. Inorganic Filler The resin composition for semiconductor encapsulation of the present invention contains the polyether copolymer and an inorganic filler.

Examples of the inorganic filler to be blended into the polyether copolymer include calcium carbonate, silicon dioxide
Examples include fused silica, crystalline silica), alumina, and talc.

These inorganic fillers may be used alone or in combination of two or more.

The particle size of the inorganic filler may be 5 gm or less, and preferably finer particles are used.

The type and particle size of the inorganic filler may be appropriately selected depending on the type of semiconductor to be used.

The surface of the inorganic filler to be blended may be subjected to a suitable treatment agent.

In the present invention, the blending ratio of the inorganic filler to the polyether copolymer is In to 80% by weight,
It is important that the content is preferably 20 to 55% by weight.

If the blending ratio of the inorganic filler is less than 10% χ, the thermal expansion coefficient of the obtained polyether copolymer assembly IIt will be high and the thermal conductivity will be low, leading to cracks due to temperature shock. be.

If the blending ratio exceeds 80% by weight, kneading becomes difficult and uniform mixing cannot be achieved, and the resulting polyether copolymer composition has poor fluidity.

Botether copolymer composition obtained by adding an inorganic filler to a polyether copolymer,
It is possible to increase the thermal conductivity and decrease the linear 11 tatami coefficient.

Method for molding one large package: The resin composition for semiconductor encapsulation of the present invention can be obtained by blending the inorganic filler with the polyether copolymer and subjecting the mixture to R-rubbing.

For example, a predetermined amount of an inorganic filler is mixed into a polyether copolymer powder obtained by the above-described method for producing a polyether copolymer, blended, and then pelletized using an extruder.

To encapsulate a semiconductor, the polyether copolymer beleft is fed into a molding machine, the pre-formed electronic components are placed in a mold, and the polyether copolymer is injection molded into this mold. It can be done by doing something.

Encapsulation molding is performed at a resin temperature of 350 to 450°C and a mold temperature of 150 to 250°C.

The resin composition for semiconductor encapsulation obtained in this way has high fluidity and soldering heat resistance, high thermal conductivity, low linear expansion coefficient, heat resistance, crack resistance, and moisture resistance. It is a resin composition for semiconductor encapsulation with excellent properties, and can be suitably used in the electrical and electronic fields.

[Example] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) 1,548 g of 2,6-cyclohenzonitrile was placed in a reactor with an internal volume of 200 g, equipped with a Dean-Starck trap filled with toluene, a stirring device, and an argon gas blowing tube.
g, (9 mol 14.4 hyphenol 5,580 (
30 mol), potassium carbonate 4.561 (33 mol)
and 50 IL of N-methyl-2-pyrrolidone, and heated from room temperature for 1 hour using argon gas blowing.
The temperature was raised to 95°C.

After raising the temperature, a small amount of toluene was added and the produced water was removed by azeotropy.

Next, after carrying out a reaction at a temperature of 195°C for 30 minutes, 4,4'-difluorobenzophenone 4.582
g (21 mol) to N-methyl-2-pyrrolidone 70
Further, the dissolved solution was added and the reaction was continued for an additional 40 minutes.

After the reaction was completed, the product was pulverized, washed with water and methanol in that order, and then dried to obtain 10.0 kg (yield: 98%) of a white powdery copolymer.

When the properties of this copolymer were determined, the glass transition temperature was 172°C, the crystal melting point was 365°C, and the thermal decomposition onset temperature was 560°C (5% weight loss of 1 in air).

Using Toyo Seiki Seisakusho MtJ's Capirocrav, 40
The solution viscosity was measured at a shear rate of 1,000 sec-1 at 0°C.

This copolymer has the following repeating units.

(II) (I)/((I)+(■)) = 0.3 This boether copolymer and Toshiba Ceramic's melting force (GR
-80) to a content of 50% by weight, extrusion molded at a temperature of 180'C using a twin screw extruder (manufactured by Ikegai Tekko Co., Ltd.: PCM-30), and formed into pellets. did.

This resin composition was mixed at a barrel temperature of 385°C and a mold temperature of 195°C.
An IC substrate was inserted and injection molded at ℃.

The resulting semiconductor-sealed electronic material was evaluated for crack resistance, soldering heat resistance, and moisture resistance.

■Crack resistance IT value -70 to +200 using thermal shock tester (manufactured by E&M)
Evaluation sample 3 was subjected to 50 cooling and heating cycles in the range
The occurrence of cracks in 0 pieces was measured.

■Evaluation of Solder Heat Resistance There was no change in soldering made by Tahai Co., Ltd. when the above-mentioned sealed electronic material was immersed in solder at 280°C for 30 seconds using a tester.

■ Moisture resistance evaluation in a constant temperature and humidity chamber (burn-in treatment equipment, manufactured by Tahai ■)
After 500 hours at 1.2 V (bias) under conditions of 5° C. and 98% RH, the number of defects among the 30 devices was examined.

These results are shown in Table 1.

(Example 2) Example 1 was carried out in the same manner as in Example 1, except that the content of fused silica was changed to 20% by weight.

The evaluation results are shown in Table 1.

(Example 3) The amount of raw materials charged during copolymer production in Example 1 was changed to 2,
1,290 g of 6-cyclobenzonitrile (7,5
mol), potassium carbonate 4,976 g (36 mol).

4.4'-difluorobenzophenone 4,910 g
A copolymer consisting of the following structural unit was obtained in the same manner as in Example 1, except that the amount was changed to (22.5 mol).

(I) (n) (1)/((1)+(II))=0.25 The glass transition temperature of this polyether copolymer is 170°C, the crystal melting point is 362°C, and the thermal decomposition onset temperature is 556°C. It was ℃.

This polyether copolymer was blended with the fused silica at a content of 50% by weight, and evaluated in the same manner as in Example 1.

The evaluation results are shown in Table 1.

(Example 4) The procedure of Example 3 was repeated except that the amount of fused silica was adjusted to 20% by weight. Evaluation results first
Shown in the table.

(Example 5) The same procedure as in Example 3 was carried out except that the amount of fused silica was adjusted to a content ratio of 6,517,171%.

The evaluation results are shown in table w41.

(Comparative Example 1) The same evaluation as in Example 1 was performed on the Botether copolymer produced in Example 1 without adding an inorganic filler.

The evaluation results are shown in Table 1.

(Comparative Example 2) When an inorganic filler was added to the polyether copolymer produced in Example 1 at a content of 85% by weight, extrusion molding could not be performed.

Table 1 [Effects of the Invention] The resin composition for semiconductor encapsulation of the present invention has excellent fluidity, high thermal conductivity, low coefficient of linear expansion, high heat resistance, and excellent crack resistance and moisture resistance.

The resin composition for semiconductor encapsulation of the present invention can be suitably used in the electrical and electronic fields, and can be used, for example, as a semiconductor encapsulation material for transistors, ICs, and the like.

Can you use this resin composition for semiconductor encapsulation to make transistors or ICs? Sealing it can greatly extend its lifespan.

Relationship with Procedural Amendment No. 119025 of 1990 dated 7th of 1991 Patent applicant address 1-1 Marunoshiratama-chome, Chiyoda-ku, Tokyo Name Idemitsu Kosan Co., Ltd. Representative Idemitsu Introduced patent applicant Idemitsu Kosan Co., Ltd. Agent Patent attorney Naoki Fukumura 4, Agent address: 5 Nishi-Shinjuku 7-18-20, Shinjuku-ku, Tokyo, Date of amendment order: 6, Not subject to amendment / Voluntary method Column 7, "Explanation", contents of amendment (1) The formula described in the bottom line of page 6 of Specification S is corrected.

(2) rO, 1s~0 as described in page 11, line 6 of the specification
．． 35," is corrected to rO,ls~0.40,".

(3) From page 17, line 2 of the specification: "Is it the thermal decomposition start temperature" written in jg line 3 is corrected to "is it the thermal decomposition start temperature?"

that's all

Claims (1)

[Claims] (1) The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼The repeating unit represented by (I) and the following formula (II); ▲There are mathematical formulas, chemical formulas, tables, etc.▼Represented by (II) The content ratio of the repeating unit represented by the formula (I) [molar ratio; (I)/{
(I)+(II)}] is 0.15 to 0.4, and the melt viscosity at a temperature of 400°C and a shear rate of 1,000 seconds^-^1 is less than 1,000 poise. The content ratio of the inorganic filler to the polymer is 1
A resin composition for semiconductor encapsulation, characterized in that the resin composition is blended in an amount of 0 to 80% by weight.