JPH0362845A - Semiconductor-sealing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in soldering heat resistance and moisture resistance reliability and suitable for sealing various electronic parts by blending an inorganic filler surface treated with a specified silane compound and a specified silane coupling agent. CONSTITUTION:With (A) an epoxy resin (B) a phenol type hardener is blended so that the ratio of phenolic hydroxyl groups of the hardener to epoxy groups of the epoxy resin may be 0.5-1.5, preferably 0.7-1.2. To 100 pts.wt. of the resultant mixture, (C) 150-700 pts.wt. inorganic filler (e.g. crystalline silica or molten silica) treated with an alkoxysilane compound represented by formula l [(n) is 1-10; R1 is formula II ((m) is 0-5); R2 is formula III ((l) is 0-5)] and one or more silane coupling agents having a functional group selected from epoxy group, amino group, etc., in the molecule is added.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition for semiconductor encapsulation that has excellent solder heat resistance, button and moisture resistance reliability.

<Prior Art> In recent years, most semiconductors have been encapsulated with resin, and epoxy resin compositions have become common in view of their normal humidity with elements and cost. Inorganic fillers such as silica are mainly used as fillers due to their mechanical properties, electrical properties, thermal properties, water resistance, and easy availability.

In recent years, as electronic components have become smaller and thinner, the semiconductor mounting method has been shifting from the conventional pin insertion method to the surface mounting method. In this case, the semiconductor is processed at high temperatures, such as by being immersed in a solder bath, during mounting, but problems have been pointed out, such as cracks occurring in the encapsulating resin and reduced moisture resistance.

To solve this problem of rack generation, various studies have been carried out in the past.
02145), a method for equalizing stress and strain by controlling the particle size (Japanese Patent Laid-Open No. 60-1
71750, Japanese Unexamined Patent Publication No. 17937/1983), but these are not necessarily sufficient.

<Problems to be solved by the invention> On the other hand, stool fat and inorganic fillers are essentially incompatible;
Various coupling agents and surface treatment methods have been developed, but none have been found to be completely satisfactory.

The present invention is intended to solve such drawbacks, and is intended to be used as a resin composition used for encapsulating semiconductors, especially as a surface treatment agent for inorganic fillers. The object of the present invention is to provide a resin composition for semiconductor encapsulation that has excellent solder heat resistance during mounting and excellent moisture resistance reliability by using at least one silane coupling agent having a group of .

<Means for Solving the Problems> That is, the present invention provides a composition containing at least an epoxy resin, a phenolic curing agent, and an inorganic filler, in which the inorganic filler is represented by the following general formula [1] ( 3) A semiconductor characterized by being treated with an alkoxysilane compound, p, and at least one silane coupling agent having a group selected from epoxy groups, amino groups, ureido groups, and mercapto groups in the molecule. The present invention relates to a sealing resin composition.

(R,○)3 S l(CH2) nS l(○R2)
3 l11) Next, the present invention will be explained in detail.

Any epoxy resin used in the present invention can be used as long as it has two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, novolac type epoxy resin synthesized from various phenolic resins, naphthalene 1,6-sibricidyl ether, 4,
4-bis(2,3-epoxypropoxy)! , 3,5゜5-tetramethylbiphenyl, glycysol ester type epoxy resin, glycysilane type epoxy (4) resin, chain aliphatic epoxy resin, trifunctional epoxy resin,
Examples include tetrafunctional epoxy resins and epoxy resins into which halogens such as chlorine and bromine are introduced, and one or more of these may be used. Among these, cresol novolak type epoxy resins, phenol novolac type epoxy resins, and 4,4-bis(2,3-epoxypropoxy)-3,3,5,5-tetramethylbiphenyl are preferred.

The fewer ionic impurities and components that easily decompose into ions in these epoxy resins, the better! Specifically, free sodium ions and chlorine ions are each 5
ppm or less and hydrolyzable halogens are 5 o o pp
I prefer m or less! Yes. Epoxy equivalent is 160 to 250,
Especially 160 to 210 is good. The resin used has a softening point of 50 to 110°C.

As the phenolic curing agent used in the present invention, one having at least two or more hydroxyl groups in one molecule is used. For example, phenol, resorcinol, cresol, xylenol, propylphenol, amylphenol, phthylphenol, octylphenol, phenylphenol, allylphenol, bisphenol Al, etc. are synthesized singly or in combination with novolak resin, polyisozorobenylphenol, etc. , polyvinyl phenols, and phenol-type choking agents in which no-logen groups are introduced, and one or more of these may be used. Among these, if the amount of uncondensed phenolic compound is less than 1 layer, it is good! 〈is 0.
Novolak resins having a weight φ of 5 or less are suitable. The softening point used is 50 to 110°C.

The blending amount of the phenolic curing agent is such that the ratio of the phenolic hydroxyl group of the curing agent to the epoxy group of the epoxy resin is 0.5 to 1.
It is preferably in the range of 5, particularly preferably in the range of 0.7 to 1.2. If it is outside the above range, it is not preferable because it lowers the moisture resistance reliability.

Furthermore, the inorganic filler used in the present invention may be at least one of spherical, egg-shaped, gourd-shaped, scale-shaped, whisker-shaped, ring-shaped, or rod-shaped, which does not substantially have a fractured surface, and Specifically speaking, the filler includes crystalline silica, fused silica,
Examples include titanium oxide, alumina, magnesia, Merck, calcium silicate, calcium carbonate, and magnesium sulfate. Crystalline silica and fused silica are usually preferred.

The inorganic filler having substantially no fractured surface can be produced by pulverizing lumps of crystalline silica, fused silica, alumina, calcium silicate, Merck, calcium carbonate, etc. using a ball mill, vibration mill, etc. There is a method of producing powders by blowing them into a flame or plasma at a temperature that melts them, melting only or the entire surface, and then cooling.

In the case of silica, S I Hn C' 4- n
It can also be produced by subjecting a silane compound represented by (n: an integer of 0 to 4) to high-temperature hydrolysis or high-temperature oxidation, spheroidizing the resulting synthetic silica fine powder by spray granulation, and firing or melting it. can.

(7) Furthermore, the average particle size of the inorganic filler is 0.5 to 150 μm, preferably 1 to 60 μm. If the average particle size is less than 0.5 μm, the fluidity of the composition during melting will decrease, resulting in
If it exceeds 0 μm, the mold may not be filled or the wire may flow during molding.

Further, the specific surface area of the inorganic filler is 0.1 to 15 m''/
Preferably, it is 0-5 to 10 m2/g. If the specific surface area is less than 0.1 m''/g, the filling structure of the filler will be poor, and the moldability, especially the crispiness, will be deteriorated.
If it exceeds 5 m27 g, the fluidity of the composition during melting will decrease, causing a problem.

Generally, the blending ratio of the inorganic filler to the resin content is preferably 150 to 700 parts by weight per 100 parts by weight of the resin content, which is the combined epoxy resin and curing agent.

If the amount is less than 150 parts by weight, the thermal shock resistance, thermal conductivity and thermal expansion properties will not be sufficiently improved, and if it exceeds 700 parts by weight, the fluidity during melting will decrease, which poses a problem.

The alkoxy(8) silane compound having a specific structure used in the present invention is a compound having a structure represented by the general formula [1] (R,○)zsi(CH2)n81(ORz)3CD. Or n-1 to 5,
m=i~3, t=1~3. Examples of such compounds include 1,2-bis(trimethoxysilyl)ethane.

The silane coupling agent of the present invention includes at least one silane coupling agent having any one of an epoxy group, an amino group, a ureido group, and a mercapto group in the molecule.
Seeds can be used.

Examples of such silane coupling agents include γ-glycidyloxyzolobyltrimethoxysilane, γ-glycidyloxyprobyltriethoxysilane, γ-glycidyloxypropylmethylzomethoxysilane, γ-glycidyloxypropyl methyl silane, Toxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, [(3,
4-Epoxycyclohexyl)ethylcomethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ
-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminozolopyltrimethoxysilane, N-
β(aminoethyl)r-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminozolopylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyljethoxysilane, N-phenyl-γ
Aminopropyltrimethoxysilane, N-phenyl-γ
Examples include -aminozolotriethoxysilane, γ-ureidonorobyltriethoxysilane, r-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and r-mercaptopropyltriethoxysilane.

In the present invention, an alkoxysilane compound having a specific structure represented by the general formula [1] used to treat an inorganic filler and an epoxy group, an amino group, a ureido group,
The mixing ratio of the silane coupling agent having at least one type of mercapto group is usually from 0.1 to 0.1 by weight.
It is preferable to use a range of 10. That is, if the amount added is outside of this range, the effect of improving moisture resistance reliability and soldering heat resistance is poor.

Silane coupling with an alkoxysilane compound having a specific structure represented by general formula [1] (hereinafter referred to as a silane compound) and having at least one of an epoxy group, an amino group, a ureido group, and a mercapto group in the molecule The amount of the mixture of coupling agents (hereinafter referred to as coupling agents) varies depending on the average particle size, surface condition, specific surface area, etc. of the inorganic filler, but is usually 0.0 parts by weight of each inorganic filler.
It is preferable to use it in a range of 1 to 10 parts by weight! Yes. That is, outside the range of the addition amount, the effect of improving moisture resistance and soldering heat resistance will hardly be recognized.

According to the present invention, a method of treating an inorganic filler with a silane compound and a coupling agent includes, for example, dissolving these in water or an organic solvent, mixing them with the whole inorganic filler, leaving them for a while, filtering and drying. method, method of distilling off the solvent by heating or reduced pressure and drying method, method of directly contacting and mixing the silane compound, coupling agent, and inorganic filler without using a solvent, and coupling with the silane compound without using a solvent. A method in which the silane compound and the coupling agent are mixed together or each dissolved in water or an organic solvent with the inorganic filler, and then the silane compound and the coupling agent are mixed together with the inorganic filler, and the silane compound and the coupling agent are mixed together with the inorganic filler, It can be carried out by a conventional method such as processing in a ball mill and then drying.

Other methods for treating inorganic fillers include a method of mixing a silane compound and a coupling agent (IL) and treating the inorganic filler at the same time, and treating the inorganic filler with a silane compound and then treating the inorganic filler with a coupling agent. Any method can be applied, including treating the inorganic filler with a coupling agent and then treating it with a silane compound.

These treated inorganic fillers, epoxy resins, and curing agents can be uniformly kneaded into a composition using a roll, a kneader, etc., a melt mixing method, a solution method, or the like.

The composition of the present invention optionally contains triphenylphosphine, 1,8-zoatehycyclo[5°4.0)-7-
Value accelerators such as undecene and its salts, release agents such as Hoechst wax and carnauba wax, colorants, flame retardants, flame retardant aids, and the like can be added.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A mixture of 0.25 g of 1,2-bis(trimethoxysilyl)ethane and 2.25 g of Fgamma-glycidoxyglobyltrimethoxysilane per 100 parts by weight of the inorganic filler was mixed with fused silica (commercial product). FS-892 (manufactured by Denki Kagaku Kogyo Co., Ltd.) and mixed well. After processing this material in a Henschel mixer for 6 minutes at room temperature, it was heated to 70°C.
, heated for 2 hours.

480 g of the above-treated fused silica and 4,4'-bis(2,6-nipoxypropoxy)-6 with an epoxy value of 18,
○H to 95g of 5',5.5'-tetramethylpiphenyl
45g of f1ffi105 phenol novolak resin,
Furthermore, triphenylphosphine 1.8 is used as a curing catalyst.
8g, add 82.56g of Hoechst L Knox, 100g
After melt-kneading with rolls at 0.degree. C., the mixture was cooled and pulverized to obtain a -C resin composite.

This resin composition was molded by low pressure transfer molding at 170°C for 2.5 minutes to obtain an 80 pin Q, FP with a simulated element sealed therein.
Time post cured. After post-curing, the solder heat resistance and moisture resistance reliability of each resin composition were measured using the following measuring method. The results are shown in the table.

Example 2 A product was treated in exactly the same manner as in Example 1 except that 2.25 g of γ-aminozolopyltrimethoxysilane was used instead of 2.25 g of γ-glycidyloxyglobiltrimethoxysilane. A composition was obtained. The measurement results of solder heat resistance and moisture resistance reliability are shown in the table.

Example 5 A composition was prepared in exactly the same manner as in Example 1 except that 2.25 g of γ-ureidopropyltrimethoxysilane and Vk were used in place of 2.25 g of γ-glycisyloxypropyltrimethoxysilane. I got something. The d111 constant results of solder heat resistance p and fM reliability are shown in the table.

Example 4 The same procedure as in Example 1 was carried out except that 2.25 g of r-mercazotozolobyltrimethoxysilane was used in place of 2.25 g of γ-glycyzologyciglobiltrimethoxysilane. A composition was obtained. The measurement results of solder heat resistance p and moisture resistance reliability are shown in the table.

Example 5 Similar to Example 1, 5 g of γ-glycidyloxyprobyltrimethoxysilane IA and 1.15 g of γ-aminozorobyltrimethoxysilane were used in place of 2.25 g of γ-glycysiloxyprobyltrimethoxysilane. A composition was obtained by processing in exactly the same manner except that . The measurement results of solder heat resistance and moisture resistance reliability are shown in the table.

Example 6 In Example 1, 1,2-bis(trimethoxysilyl)ethane 0.25F and 2.25 g of (γ-cricidyloxyprobyl)trimethoxysilane were replaced with 1,2-bis( Trimethoxysilyl)ethane 0.50g, (γ-glycidyloxyglobil)trimethoxysilane 2.00
A composition was obtained by processing in exactly the same manner except that g was used. The measurement results of solder heat resistance and moisture resistance reliability are shown in the table.

Example 7 Fused silica (trade name FS-892: M, manufactured by Keikagaku Kogyo Co., Ltd.) was added at a ratio of 0.25 g of 1,2-bis(trimethoxysilyl)ethane to 100 parts by weight of the inorganic filler. Add and mix well. Mix this in a Henschel mixer.
After processing at room temperature for 5 minutes, it was heated at 70°C for 2 hours. 2.25 F of (γ-glycisyloxyprobyl)trimethoxysilane was added to the obtained treated filler and mixed well. This was further treated in a Henschel mixer at room temperature for 5 minutes, and then heated for 70'O-2 hours.

480g of the above-treated silica and 4 with an epoxy value of 186,
4'-bis(2,3-epoxypropoxy)-5,5,
5,5-tetramethylbiphenyl 95F17i:0H(
45g of phenol novolac resin of iffi103, and triphenylphosphine i, ss as a curing catalyst.
g and 82.56 g of Hoechst wax were added thereto, and the mixture was melt-kneaded using rolls at 100° C., cooled and pulverized to obtain a resin composition.

Using this resin composition, molding was performed at 170°C for 2.5 minutes using a low-pressure transfer molding method to obtain 80 pin Q and FP with side-stopped simulated elements.
Time post cured. After post-curing, the solder heat resistance and moisture resistance reliability of each resin composition were measured using the following measuring method. The results are shown in the table.

Comparative Examples 1 to 5 Fused silica that was not subjected to silane treatment, and fused silica that was treated with a silane cutting agent only using 2.25 g of (γ-glycisyloxypropyl)trimethoxysilane in Example 1; A composition similar to that in Example 1 was obtained using fused silica treated only with 0.25 g of 1.2-bix<+-rimethoxysilyl)ethane. Perform the operation and seal molding 8
The soldering heat resistance and humidity resistance reliability were measured. The results are summarized and shown in Table 1.

Method for measuring solder heat resistance: Six 80-pin QFPs were treated at 85°C/85%RH for 72 hours and 96 hours, then treated with Paper Phase Reflow 21500 for 90 seconds, and the percentage of packages with cracks was determined. Ta.

Measuring method for moisture resistance reliability: In order to investigate the corrosion of aluminum metal electrodes, 20 pieces of 80 ptn QFP coated with a molded semiconductor element were placed in a pressure cooker (121°C, 12abm, 100% R,T).
() Aluminum corrosion after being left for 500 hours was investigated. Failure was determined by the occurrence of an open aluminum pattern or an increase in leakage current beyond a certain limit.

1) GPT: γ-glycisyloxypropyltrimethoxysilane APT: γ-aminozolopyltrimethoxysilane TJPT: γ-ureidopropyltrimethoxysilane MPT 2 γ-mercaptozolopyltrimethoxysilane BTE: n = 2, m = # = 1 2) Number of defectives/number of samples <Effects of the invention> Above and S-t) The epoxy resin composition of the present invention has low solder heat resistance when used for semiconductor encapsulation and is made into a cured product. Immediately improves reliability and moisture resistance! It exhibits excellent properties and is useful as a resin for encapsulating various electronic components.

Claims (1)

[Claims] (1) In a composition containing at least an epoxy resin, a phenolic curing agent, and an inorganic filler, the inorganic filler is an alkoxysilane compound represented by the following general formula [1], and an epoxy group, an amino group in the molecule, 1. A resin composition for semiconductor encapsulation, which is treated with at least one silane coupling agent having a group selected from a ureido group and a mercapto group. ((R_1O)_3Si(CH_2)_nSi(OR_
2)_3 [1] n: Integer from 1 to 10 R_1: C_mH_2_m_+_1 (m is an integer from 0 to 5) R_2: ClH_2_l_+_1 (l is an integer from 0 to 5))