JPH01204953A - Resin composition for semiconductor sealing - Google Patents

Abstract

PURPOSE:To provide a resin composition for semiconductor sealing, small in a stress generated by a change in temperature or the like and capable of absorbing a stress generated, by mixing an epoxy resin with a curing agent and an inorganic filler surface-treated with a specified silane compound. CONSTITUTION:An inorganic filler (e.g., silica or alumina) is mixed with a compound of formula I (wherein R<1>-R<8> are each a monovalent hydrocarbon group having at least one group of formula II and at least one reactive organic group or H, R<9> is O or a bivalent organic group, R<10> is H or a monovalent hydrocarbon group, and m>=0), e.g., formula III, with a high-speed mixer or the like to surface-treat the inorganic filler with the compound of formula I. The surface-treated inorganic filler is mixed with an epoxy resin (e.g., bisphenol A epoxy resin), a curing agent (e.g., novolac phenolic resin) and necessary additives (e.g., flame retardant or colorant) to produce a resin composition for semiconductor sealing.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a resin composition for semiconductor encapsulation, and in particular to a resin composition for reducing the stress applied to a chip and improving its reliability when encapsulating a semiconductor with a resin. The present invention relates to a resin composition for semiconductor encapsulation.

[Conventional technology]

Cured epoxy resins have excellent electrical properties, heat resistance, mechanical properties, moisture resistance, etc., and have thus far been widely used for sealing electrical and electronic components. In particular, as a resin sealing material for transistors, ICs, LSIs, etc., it is extremely inexpensive compared to conventional metals and ceramics, and is also superior in terms of performance and reliability.

[Problem to be solved by the invention]

In recent years, in the field of semiconductors, the rate of increase in the degree of integration has been extremely rapid, the size of devices has become larger, and the properties required of sealing materials have become stricter. Particularly in resin encapsulation, stress caused by expansion or contraction of the resin due to temperature changes not only changes or degrades the performance of the semiconductor element, but also causes damage to the passivation film, significantly reducing moisture resistance. Therefore, it is desired to develop a resin composition that can be used as a sealing material and can minimize the generation of stress due to temperature changes and the like, and can absorb as much of the generated stress as possible.

An object of the present invention is to provide a resin composition for semiconductor encapsulation that is extremely resistant to expansion or contraction caused by temperature changes or the like.

[Means to solve the problem]

The present invention provides a resin composition for semiconductor encapsulation which is mainly composed of an epoxy resin containing an inorganic filler, in which the inorganic filler is expressed by the following general formula (1) (where m≧0SR1, R2,
...R8 is -R9-S t
(OR10) 3 groups and 1 reactive organic group each
R9 is oxygen or a divalent organic group, and R10 is hydrogen or a monovalent hydrocarbon group. This is a resin composition for semiconductor encapsulation.

[Function] When the compound represented by the general formula (1) is surface-treated on an inorganic filler, the alkoxy groups in the compound are hydrolyzed and chemically bonded to the inorganic filler. The organic residues chemically bond with the epoxy resin/hardener system. Therefore, this compound is interposed between the inorganic filler and the cured epoxy resin, contributes to absorbing the stress that occurs, and provides a resin composition for semiconductor encapsulation that is extremely resistant to the effects of expansion or contraction due to temperature changes, etc. .

The compound of general formula (I) used in the present invention can be synthesized, for example, by reacting a siloxane oligomer with hexamethyldisiloxane to obtain an H-modified silicone polymer, and then hydrosilylating this.

m in formula (I) is preferably 10 or more.

Also, on days R1 to R, one or more -R9-
3i (OR10) Hydrocarbon group or hydrogen having three groups and a reactive organic group. The reactive organic group is preferably 3-glycidoxypropyl group, 2-(
3,4-epoxycyclohexyl)ethyl group, 3-aminopropyl group, fl-(2-aminoethyl)3-aminopropyl group, 3-mercaptopropyl group, vinyl group, aryl group or/and 3-methacryloxypropyl group is preferred. Among these, 3-glycidoxypropyl group and 2-(3,4-epoxycyclohexyl)ethyl group are particularly preferred, and 3-aminopropyl group and n-(
2-aminoethyl)3-aminopropyl group and 3-mercaptopropyl group are also effective.

Groups other than the specific groups R1 to R8 are hydrocarbon groups,
Generally, methyl group, phenyl group, etc. are preferred.

-R9-3i (OR10) The three R9 groups are preferably an ethylene group, and R10 is preferably a methyl group or an ethyl group. Specific examples of such groups include trimethoxysilyl group, trimethoxysiloxy group, trimethoxysilylalkyl group, triethoxysiloxy group, triethoxysilylalkyl group, tris(2-methoxyethoxy)siloxy group, tris(2-methoxyethoxy)siloxy group, and tris(2-methoxyethoxy)siloxy group. -methoxyethoxy)silylalkyl group is preferred.

Inorganic fillers used in the present invention include quartz, zirconia, wollastonite, talc, mica, alumina,
Examples include crystalline silica and amorphous silica, and among these, silica is particularly preferred.

The compound represented by the general formula (1) is added at a rate of 0.01 to 5% by weight to the inorganic filler, and the surface of the inorganic filler is chemically treated.

The method for treating the inorganic filler is as follows: - Inject an appropriate amount of the inorganic filler into a high-speed fluid stirring mixer such as a Henschel mixer or a super mixer, and (1) add a predetermined amount of the treatment agent as a undiluted solution. (2) Dilute the treatment agent with an organic solvent/water mixture, such as ethanol/water: 9 Q/I 0% by weight. After that, a predetermined amount is dropped onto the inorganic filler powder fluidized by the stirring mixer, stirred at high speed for 3 to 10 minutes, and then heated and dried using a hopper dryer to remove moisture, solvent, etc. .

In the present invention, the epoxy resin to which the inorganic filler surface-treated with the compound of general formula (I) is added is 1
Any resin may be used as long as it has two or more epoxy groups in the molecule, and specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, Talesol novolac type epoxy resin,
Examples include arylphenol novolak type epoxy resins, alicyclic type epoxy resins typified by epoxy resins having a cyclohexene oxide group, halogenated bisphenol type epoxy resins, and halogenated phenol novolac type epoxy resins. The bonding mode of the glycidyl groups in these epoxy resins may be any of ether type, ester type, and amine type, and is not limited to a specific type. Further, two or more of these epoxy resins may be used in combination; - For boat fishing, it is preferable to use a cresol novolak type epoxy resin and a brominated phenol novolac type epoxy resin in combination.

When using a novolac type phenol resin, bisphenol A1 bisphenol F, etc. as a curing agent for the epoxy resin, any compound having two or more phenolic OH groups in one molecule may be used. In addition to these, as a curing agent, for example, fucuric anhydride, hexahydrophthalic anhydride, trimellitic anhydride, methylnadic anhydride, etc. can be used. Two or more types can be used together.

The additives that can be included in the resin composition of the present invention include those that can be used in this type of resin composition, but generally include flame retardant aids, colorants, mold release agents, etc. A hardening agent and a curing accelerator are added.

First, antimony oxide is used as a flame retardant aid, carbon blank is used as a coloring agent, and carnauba wax is used as a mold release agent.
Moncnic acid ester, stearic acid, C of stearic acid
a, Zns Metal salts such as Mg and Af, etc., and as curing accelerators, imidazole compounds, phosphines such as triphenylphosphine and tributylphosphine, and 1,8-diazabicyclo(5,4,O) undecene. -7 etc. can be given. Furthermore, as other additives, a silane coupling agent, a deterioration inhibitor, an ionic substance scavenger, etc. can be added as appropriate.

A general method for manufacturing a semiconductor encapsulant using the above resin composition is to thoroughly mix the above resin composition in fine powder form at an appropriate blending ratio, and then use a kneader or hot roll etc. for a short period of time, immediately cool rapidly to stop the curing reaction at an appropriate stage, crush and tablet, generally at 5°C.
Store below.

After returning this tablet to room temperature, high frequency
It is preheated to 90°C, placed in a pot of a transfer molding machine, and molded into a predetermined shape using various molds.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Production Example 1 (-Production of maximum (1) compound) Stirring device,
In a glass flask equipped with a condenser and thermometer, add 1.8 moles (482 g) of silicone oligomer (II).
), hexamethyldisiloxane 0.5 mol (81 g)
, 2.1 g of activated clay was charged, the temperature was raised to 70°C, and the mixture was heated and stirred for 24 hours. After cooling this reaction solution to room temperature, the activated clay was removed by vacuum filtration, and the low-boiling components in the furnace solution were heated to 150°C.
Distillation was carried out under conditions of 1 Hg/Hg to obtain 480 g (yield: 85.3%) of H-modified silicone polymer (■).

0.4 mol (467 g) of the above H-modified silicone polymer
was charged into a glass flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, and the temperature was raised to 120°C.
6 g) and 0.4 mol (5 mol) of vinyltrimethoxysilane
9.2g), 11% chloroplatinic acid isopropanol solution '1
A mol (111 .mu.) of (12,4×10−) was placed in a dropping funnel, and added dropwise over 1 hour to the H-modified silicone polymer kept at 120° C. with stirring, and further aged at 120° C. for 1 hour.

Thereafter, low-boiling components were distilled off from the reaction solution at 100°C/l mm Hg, and 523g (91.4%) of compound S1 was obtained.
I got it. In this compound S1, m in the general formula is 15 on average.
．． It was found that this compound has an average of one trimethoxysilyl group and one glycidoxyprobyl group in each molecule.

Production Example 2 In Production Example 1, 0.8 mole (91.2 g) was used instead of 0.4 mole of aryl glycidyl ether, and 0.8 mole (118 g) was used instead of 0.4 mole of vinyltrimethoxysilane.
Compound S2 was synthesized in the same manner as in Production Example 1 except that g> was used. In this compound S2, m in the general formula is 15 on average.
It was found that the compound has an average of two trimethoxysilyl groups and two glycidoxyprobyl groups in one molecule.

Production Example 3 Compound S3 was synthesized in the same manner as Production Example 1 except that 0.25 mole (40.5 g) of hexamethyldisiloxane was used instead of 0.5 mole. In this compound S3, m in the general formula was 30 on average. Using this polymer, 2-(3゜4-epoxycyclohexyl) was used instead of 0.4 mole of aryl glycidyl ether.
Compound S3 was obtained in the same manner as in Production Example 1 except that 0.4 mol of ethylene was used. This compound S3 was found to be a compound in which m in the general formula is 30 on average, and each molecule has one trimethoxysilyl group and one 2-(3,4-epoxycyclohexyl)ethyl group on average. .

Production Example 4 In Production Example 1, aryl glycidyl ether 0.4
0.4 mole (22
, 8g) was used in the same manner to obtain Compound S4. In this compound S4, m in the general formula is 15 on average, and 1
It was found that this compound has an average of one trimethoxysilyl group and one 3-aminopropyl group in the molecule.

The compounds 31 to S4 above have the following segments (1
) to (6), / segment (1) segment (21H2G\ CH3 segment (3) 5i-0- / segment (4) segment (5) CH3 / 2G\H2 segment (6) Its terminal are doing.

The average number of intermediate segments in one molecule of 81 to S4 is as shown in Table 1.

Below is the margin. Table 1 The sequence of segments is generally random. For example, compounds 81-
An example of S4 is as shown in the following equation.

The following margins S1: S2: CH2 / H2 \ / H2 \t't2U- (J S3: S4: CH3 \ CH2 / 2 C \ CH2 Examples 1 to 5 Compounds 81 synthesized in Production Examples 1 to 4 above A predetermined amount of ~S4 was added dropwise onto the fluidized powder of silica placed in a Henschel mixer, and high-speed stirring was performed for about 8 minutes to surface-treat the silica with the compound.

This surface-treated silica was mixed with each component of the epoxy resin composition shown in Table 2 in the proportions shown in Table 2, melt-kneaded using a kneader, and then cooled, crushed, and tableted.

Using the tablet thus obtained, a test piece was prepared using a transfer molding machine, and the cured product was evaluated. Comparative Example 1 shows a case in which silica was surface-treated using a commonly used epoxy-based silane coupling agent and an amino-based silane coupling agent for compression.
(3-glycidoxyprobyltrimethoxysilane),
Comparative example 2 (2-(3,4-epoxycyclohexyl)
(using ethyltrimethoxysilane) and Comparative Example 3 (using 3-aminopropyltriethoxysilane). These compounding compositions and evaluation results are shown in Tables 2 and 3.

*1 The bending elastic modulus E can be approximated by the following formula ΔL: ΔL=λX (Tg-TRT) =λ·Tg. Therefore, 1,°, σ#E・λ・Tg.

However, λ: Coefficient of thermal expansion (1/''C) Tg Ni-glass transition point (''C) TRT: Room temperature ('C) The smaller the values of both E1λ and Tg, the smaller the stress σ generated inside can be. However, in order to maintain heat resistance, a Tg of 150° C. or higher is required for boat fishing. As shown in Table 3, if Tg is set to around 160° C., the stress σ generated inside can be sufficiently reduced by reducing E and λ.

As is clear from the above examples, when using silica whose surface has been treated with the compound of maximum (I), compared to the case where the surface of silica is treated using a conventionally commonly used silane force/knobling agent, A decrease in the flexural modulus of the obtained resin composition (cured product) was observed, and the stress generated inside could be significantly reduced.

〔Effect of the invention〕

According to the present invention, it is possible to obtain a resin composition for semiconductor encapsulation that can minimize the occurrence of stress due to temperature changes and the like, and can absorb as much of the generated stress as possible.

Agent: Patent Attorney Kawakita Takecho

Claims (1)

[Claims] (1) In a resin composition for semiconductor encapsulation whose main components are an epoxy resin containing an inorganic filler and a curing agent thereof, the inorganic filler may be represented by the following general formula (I) ▲ Numerical formula, chemical formula,
There are tables, etc.▼(I) (In the formula, m≧0, R^1, R^2,...R^8 is one of -R^9-Si(OR^1^0)_3 groups and A monovalent hydrocarbon group or hydrogen each having one or more reactive organic groups, R^9 is oxygen or a divalent organic group, R
1. A resin composition for semiconductor encapsulation, characterized in that the resin composition is surface-treated with a compound represented by ^1^0 is hydrogen or a monovalent hydrocarbon group.