JPS62210655A - Semiconductor device - Google Patents

Abstract

PURPOSE:To obtain a device characterized by high moisture resisting reliability, excellent electric characteristic, high heat resisting reliability and less internal stress, by using an epoxy resin composition including a specified components. CONSTITUTION:An epoxy resin composition used for sealing is composed of the following materials: epoxy resin; phenol resin; and a remaining heterocyclic compound group, in which both ends of a molecule chain have at least two second-class amino group in a molecule. The composition is obtained by using a silica filler and the like, whose surface of a particle is covered with a coating layer. Its main part is an additive reaction product comprising the following materials: polydimethyl siloxane oligomer, in which the chain part of a molecule chain is coupled with nitrogen of the second-class amino group of any of the remaining end group; and a compound, which has at least two epoxy group in the molecule. Thus the highly reliable semiconductor, in which internal stress is decreased and the amount of a hardening accelerator is largely decreased or made to be zero, is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a highly reliable semiconductor device.

[Conventional technology]

Semiconductor elements such as transistors, ICs, and LSIs are usually sealed with ceramic packages, plastic packages, or the like to form semiconductor devices. The above-mentioned ceramic package has heat resistance in the constituent material itself,
It also has excellent moisture permeability, so it is resistant to temperature and humidity, and because it is a hollow package, it has high mechanical strength and can be sealed with high reliability. However, since the constituent materials are relatively expensive and the mass productivity is poor, resin sealing using the above-mentioned plastic package has recently become mainstream. Epoxy resin compositions have conventionally been used for this type of resin sealing, and have achieved good results. However, due to technological innovation in the semiconductor field, the degree of integration has increased, element sizes have become larger, and interconnects have become finer, and packages are also becoming smaller and thinner. There is a demand for further improvement in reliability (internal stress, moisture resistance reliability, shock resistance reliability, heat resistance reliability, etc. of the obtained semiconductor device).

In particular, epoxy resin compositions used for semiconductor encapsulation consist of an epoxy resin, a phenol resin as a curing agent, and a curing accelerator (mainly tertiary amines) that accelerates the reaction between the two. Curing accelerators, which are tertiary amines, exist freely in cured epoxy resins and are easily mobile at high temperatures, significantly reducing the electrical properties (especially electrical insulation) and moisture resistance of cured epoxy resins. This deteriorates the electrical characteristics and moisture resistance reliability of the semiconductor device, and therefore improvements are desired.

[Problem that the invention seeks to solve]

As mentioned above, in conventional epoxy resin compositions for sealing, a considerably large amount of curing accelerator was present, leading to a decrease in electrical properties and moisture resistance. In the process of cooling the product from the curing temperature to room temperature, considerable internal stress is generated due to shrinkage, which causes problems such as damage to semiconductor elements and disconnection of wires. In order to reduce this internal stress, addition of rubber particles, modification with liquid elastomers, etc. have been carried out, but the presence of a large amount of domains of such rubber particles in the epoxy resin matrix makes the fluidity of the epoxy resin composition There were also other drawbacks, such as a decrease in Furthermore, the curing accelerator present in a fairly large amount had an adverse effect on the electrical insulation properties of the cured epoxy resin as described above.

In this way, conventional epoxy resin compositions for sealing do not have satisfactory properties, and there are limits to the reliability of semiconductor devices using them. It is strongly desired to improve the characteristics even further in order to be able to cope with the above problems.

In order to meet these demands, a proposal was made to coat silica, which is contained in a large amount in an epoxy resin composition for sealing, with synthetic rubber and to use this synthetic rubber-coated silica as a filler (Japanese Patent Application Laid-Open No. 1983-1981). -188418). According to this proposed method, the effect of reducing internal stress can be obtained by the synthetic rubber layer present at the interface between the silica and the matrix resin while suppressing the decrease in fluidity due to the use of synthetic rubber. However, this proposed method only has the effect of reducing internal stress, and does not improve the electrical properties caused by the curing accelerator. There were problems such as restrictions. That is, the synthetic rubber is attached to the outer periphery of the silica by the binder action of the silane coupling agent,
In order to create a product with such a structure, a silane coupling agent that has a functional group that reacts with both silica and synthetic rubber is used, and the synthetic rubber also reacts with the functional group of the silane coupling agent. It is necessary to use a product that has a functional group that can

However, the above-mentioned raw materials belong to a relatively special category, and there are restrictions on the raw materials that can be used, and the production of synthetic rubber-coated silica using them is complicated. Moreover, the resulting synthetic rubber-coated silica contains the above-mentioned components and has the disadvantage that it cannot be applied to a wide range of epoxy resin compositions.

This invention was made in view of the above circumstances, and it is possible to reduce the internal stress in the epoxy resin composition used for resin sealing, and at the same time, to significantly reduce or eliminate the amount of curing accelerator, thereby achieving excellent results. The purpose is to provide a reliable semiconductor device.

[Means for solving problems]

In order to achieve the above object, the semiconductor device of the present invention includes:
A configuration is adopted in which a semiconductor element is sealed using an epoxy resin composition containing the following components (A), (B), and (C).

(A) Epoxy resin.

(B) Phenol resin.

(C) Both ends of the molecular chain are composed of residues of a heterocyclic compound having at least two secondary amino groups in the molecule, and the chain portion of the molecular chain is composed of residues of a heterocyclic compound having at least two secondary amino groups in the molecule, and the chain portion of the molecular chain is Silica filling whose particle surface is coated with a coating layer mainly composed of an addition reaction product of a polydimethylsiloxane oligomer bonded to the nitrogen of a secondary amino group and a compound having at least two epoxy groups in the molecule. agent.

That is, this invention uses silica whose particle surface is coated with a coating layer mainly composed of the above-mentioned addition reaction product as component C, and this silica is coated with a binder like the above-mentioned synthetic rubber-coated silica. There is no need to bond the layer to the silica surface, so there is a wide degree of freedom in selecting raw materials, and manufacturing is easy. Furthermore, it does not contain a binder component and can be applied to a wide range of epoxy resin compositions. As a result, according to the present invention, there is no complication of the process when manufacturing semiconductor devices, and the use of the silica filler as component C not only reduces internal stress but also significantly reduces the amount of curing accelerator. It becomes possible to realize the elimination of such defects, thereby making it possible to significantly improve the reliability of semiconductor devices.

The epoxy resin composition used in this invention consists of an epoxy resin (component A), a phenol resin (component B), and a heterocyclic ring in which both ends of the molecular chain have a small number (both have two secondary amino groups) in the molecule. A polydimethylsiloxane oligomer composed of residues of a compound of the formula formula, in which the chain part of the molecular chain is bonded to the nitrogen of any secondary amino group of the terminal residue, and at least two epoxy groups in the molecule. It is obtained using a silica filler (component C) whose particle surface is coated with a coating layer mainly composed of an addition reaction product with a compound having In addition, the above "oligomer" is
The term is used to include dimers.

The epoxy resin serving as the above A component is not particularly limited, and various epoxy resins conventionally used as encapsulating resins for semiconductor devices can be mentioned, such as Talesol novolac type, phenol novolac type, and bisphenol A type. . Among these resins, those having a melting point above room temperature and exhibiting a solid rod or a highly viscous solution form at room temperature bring about good results. As a novolak type epoxy resin, usually epoxy ff1160~
250. A cresol novolak type epoxy resin having a softening point of 50-130'C (7) is generally used, and a cresol novolac type epoxy resin having an epoxy ff of 1180-21o and a softening point of 60-110°C is generally used.

The phenolic resin of component B used together with the epoxy resin acts as a curing agent for the epoxy resin, and phenol novolak, cresol novolac, etc. are preferably used. These novolak resins have a softening point of 50 to 110°C and a hydroxyl equivalent of 70 to 150.
It is preferable to use one. Particularly, among the above novolac resins, use of cresol novolac brings about good results.

The C component is a silica filler coated with a coating layer mainly composed of an addition reaction product of a specific polydimethylsiloxane oligomer as described above and a compound having at least two epoxy groups in the molecule, The polydimethylsiloxane oligomer used as the addition reaction product that forms the main part of the coating layer is composed of residues of a heterocyclic compound having at least two secondary amino groups in the molecule at both ends of the molecular chain, and It has a structure in which the chain portion of the molecular chain is bonded to the nitrogen of any of the secondary amino groups of the terminal residues. Here, the term "mainly" is intended to include cases where the entire coating layer is composed of the addition reaction product serving as the main.

As a specific example of the above-mentioned polydimethylsiloxane oligomer, when the above-mentioned heterocyclic compound residue is, for example, a piperazine residue, it is schematically represented by the following formula (a).

Examples of the heterocyclic compound residue having a secondary amino group as described above include, in addition to the piperazine residue described above, a virazolidine residue and an imidazolidine residue.

Polydimethylsiloxane oligomers as described above can be obtained by known methods. For example, ■ a reaction product of carboxypropyl-terminated disiloxane and aminoethylpiperazine (its chemical structure is as shown in formula (1) below) is prepared in advance, and this piperazine-terminated dimethylsiloxane dimer (formula (1) shown below) is prepared in advance. The equilibration polymerization of cyclic tetradimethylsiloxane into a piperazine-terminated polydimethylsiloxane oligomer (the chemical structure of which is expressed by the formula (see below))
2) can be obtained. In addition, as another method, (1) First, a cyclic tetradimethylsiloxane is added to an epoxy-terminated dimethylsiloxane dimer (the chemical structure is as shown in formula (3) below), which is a reaction product of allyl glycidyl ether and metachlorosilane. An epoxy-terminated polydimethylsiloxane oligomer (the chemical structure of which is shown in formula (4) below) is synthesized by equilibration polymerization. next,
By reacting this oligomer with a large excess of piperazine, a piperazine-terminated polydimethylsiloxane oligomer (the chemical structure of which is as shown in formula (5) below) can be obtained. Naturally, contrary to method (2), the above epoxy-terminated dimethylsiloxane dimer (formula (3))
By first reacting with a large excess of piperazine,
It is also possible to synthesize a piperazine-terminated dimethylsiloxane dimer and then obtain an oligomer by equilibration polymerization of cyclic tetradimethylsiloxane in the same manner as in method (2).

(Left below) Synthesis methods for these polydimethylsiloxane oligomers are described in many documents, but a representative example is the one published by R.S. Bauer, Epoxy Resin Chemistry n, ACS Symposium. Series, AC5 (1983) P21-P54 (Epo
xy Re5tn Chemistry II, A
C3Symposium-5eries) and is explained in detail.

As mentioned above, both ends of the molecular chain are present within the molecule at least two times.
A special polydimethyl composed of heterocyclic compound residues having secondary amino groups, in which the chain part of the molecular chain is bonded to the nitrogen of any of the secondary amino groups of the terminal residues. The siloxane oligomer has a number average molecular weight of 30,000
It is preferably less than or equal to 2000, more preferably 2000.
It is 0 or less, and most preferably 15,000 or less.

Here, the above-mentioned number average molecular weight can be determined by quantifying the terminal secondary amino group per unit weight as follows. First, 5 g of a specimen is accurately weighed and dissolved in 30 g of isopropyl alcohol. Add 2-3 drops of bromophenol blue water/ethanol solution as an indicator and
．． Titrate with IN hydrochloric acid. The end point is the point where the system changes from blue-purple to yellow.

The compound having at least two epoxy groups in the molecule that reacts with the polydimethylsiloxane oligomer as described above is not particularly limited, as long as it has at least two epoxy groups in the molecule as described above. Ru. Specific examples include bisphenol A rsorcinol, trihydroxybiphenyl, butanediol, ethylene glycol, propylene glycol, dioxanediol, endomethylene cyclohexanediol, phthalate, bisphenol-hexafluoroacetone, bisphenol PA, bisphenol F1 phloroglizine, 2,
2'-bis(3,4-epoxycyclohexyl)propane, vinylcyclohexane dioxide, diglycidyl ether such as 4,4'-di(1,2-epoxyethyl)biphenyl, 0-glycidylphenylglycidyl ether, 4. Examples include 4-di(1,2-epoxyethyl)diphenyl ether, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)-cyclohexane-m-dioxane, and the like. In addition, as trifunctional or more functional substances, glycerol, phloroglysitol,
triglycidyl ethers such as trimethylolpropane,
Triglycidyl-p-aminophenol, polyallyl glycidyl ether, 1,3.5-tri(1,2-epoxyethyl)benzene, 2.2", 4.4"-tetraglycidoxytetraphenylethane, 2. 6-(2,3
-epoxypropyl) phenylglycidyl ether, triglycidyl 4,4-bis(4-hydroxyphenyl)
Polyglycidyl ethers of pentanoic acid, triglycidyl-1,L,3-)liphenylpropane, O-cresol formaldehyde novolac, phenol formaldehyde novolac, and the like can be mentioned.

For example, the reaction between the above polydimethylsiloxane oligomer and the above compound having at least two epoxy groups in the molecule (hereinafter abbreviated as "epoxy compound") can be carried out using 1,4-dioxane as a medium (approximately It can be obtained by heating to a temperature of about 60°C and mixing as a 30% by weight solution). At this time, after the reaction is completed, 1,4-dioxane is scattered by drying under reduced pressure.

In the above reaction, the ratio of the polydimethylsiloxane oligomer to the epoxy compound is 1 per amine of the former (
X) and the latter epoxy equivalent (Y) ratio X/Y is 0.5≦
It is preferable to set so that X/Y≦2. In other words, when the polydimethylsiloxane oligomer is modified by adding an epoxy compound, its adhesion to silica is significantly improved compared to when the polydimethylsiloxane oligomer is used alone. This is because it is suitably exhibited by setting the polydimethylsiloxane oligomer and the epoxy compound in the above ratio. The reaction product obtained by such a reaction is schematically represented by the following formula (b).

(Margin) Component C used in this invention is obtained by coating the silica surface with the reaction product obtained as described above, and the silica to be coated is not particularly limited, and may be a crystalline or Both silica (crystalline silica) and amorphous silica (fused silica) can be used. It is preferable that these silicas have an average particle size of 5 to 80 μm and do not contain large particles of 100 μm or more.

Coating of silica with the above-mentioned specific reaction product can be carried out by mixing the above-mentioned reaction product and silica using an organic solvent such as toluene as a medium, filtering the mixture, and then drying under reduced pressure. In this case, the polydimethylsiloxane oligomer that is a component of the above reaction product is
Heterocyclic compound residues are introduced at both ends of the molecular chain, which significantly improves adhesion to the silica surface, allowing it to adhere to silica without using any binder components such as silane coupling agents. , which suitably coats the silica surface. In particular, in this invention, an epoxy compound is reacted with the polydimethylsiloxane oligomer to introduce an epoxy group into the polydimethylsiloxane oligomer, thereby further improving the adhesion to the silica surface.

In the present invention, the fact that silica is coated with the reaction product can be clarified by the uneven distribution of the product in the benzene-water system (simple interaction discrimination method). That is, in this method, uncoated silica is normally unevenly distributed in the aqueous phase, but the coated silica of this invention is unevenly distributed in the benzene phase. Regarding this evaluation method,
The present inventors have already established [Tsunetaka Matsumoto et al., Collected Papers of the 7th Composite Materials Symposium, 261 (197
4)].

In this way, by adding four heterocyclic compounds to both ends of the molecular chain of polydimethylsiloxane oligomer and further modifying the polydimethylsiloxane oligomer with an epoxy compound, the adhesion to the silica surface in particular is significantly improved. This phenomenon was discovered by the present inventors for the first time in the course of research, and it was found that the reaction product-coated silica, which can be applied to an extremely wide range of epoxy resin compositions and has stress reduction effects and electrical property improvement effects, can be easily produced. It became possible to obtain This is the greatest feature of this invention.

The reaction product-based coating layer that covers the surface of the silica exhibits a curing accelerating effect during the resin curing stage due to the action of the heterocyclic compound residues at both ends of the molecular chain in the polydimethylsiloxane oligomer. The action of the polydimethylsiloxane portion exerts an effect of relieving internal stress at a stage after curing, thereby realizing a highly reliable semiconductor device. In the above reaction product, the secondary amino groups at both ends of the molecular chain in the polydimethylsiloxane oligomer, which is a component thereof, easily react with epoxy groups (and the silicone compound has a high affinity for silica due to its structure). Therefore, after the resin has hardened, it remains firmly fixed at the interface between the silica and the matrix epoxy resin.Therefore, it does not move even at high temperatures, and the epoxy resin cures by the movement of the curing accelerator as in the past. To ensure the reliability of a semiconductor device without causing a deterioration in the electrical characteristics of a device.

The coating layer of the silica particles is mainly composed of the reaction product, and in some cases, a peroxide may be used in combination with the reaction product.

Peroxides used with the above polydimethylsiloxane oligomers include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, oprylyl peroxide, lauroyl peroxide, acetyl peroxide. , cyclohexene peroxide, hydroxyhebutyl peroxide, tert-butyl perbenzoate, ter
tert-butyl peracetate, tert-butyl octoate, terL-butyl peroxyisobutyrate,
Examples include tert-butylbar phthalate and the like.

When the above-mentioned peroxide is used in combination with the above-mentioned reaction product, the polydimethylsiloxane oligomer in the reaction product attached to the silica particle surface is polymerized due to the action of the peroxide, and the particle surface is quickly coated. You will get the effect of completing it.

When a peroxide and the above reaction product are used together in this manner, the amount of peroxide used is 0.00% relative to the above reaction product.
Good results can be obtained by setting the proportion to 0.02 to 1 part by weight.

The above-mentioned special reaction product alone or a mixture of this and peroxide is preferably set to be contained in an amount of 3 to 50% by weight in the epoxy resin composition (A+B) excluding the filler component. That is, if the content is out of the above range, the reliability of the resulting semiconductor device tends to decrease.

Incidentally, in the epoxy resin composition used in the present invention, a curing accelerator may be used in addition to the above-mentioned components A to C, if necessary, but the amount used can be significantly reduced or completely eliminated. That is, the epoxy resin composition used in the present invention uses the specific reaction product as described above, so that the amount of the curing accelerator used is 0 to 0.5 with respect to the total amount of the epoxy resin and the phenol resin. %, thereby making it possible to significantly improve moisture resistance, electrical properties, etc.

Examples of the curing accelerator include the following tertiary amines.

Suitable examples include quaternary ammonium salts, imidazoles, and boron compounds, and these can be used alone or in combination.

Tertiary amine triethanolamine, tetramethylhexanediamine, triethylenediamine, dimethylaniline, dimethylaminoethanol, diethylaminoethanol, 2.4
．． 6-tris(dimethylaminomethyl)phenol, N
, N-dimethylpiperazine, pyridine, picoline, ■
, 8-diaza-bicyclo(5,4,0) undecene-7
, benzyldimethylamine, 2-(dimethylamino)methylphenol quaternary ammonium salt dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethyltetradecylammonium chloride, stearyltrimethylammonium chloride imidazoles 2-methylimidazole, 2-undecylimidazole , 2-ethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole boron compounds tetraphenylboron salts such as triethyleneaminetetraphenylporate, N-methylmorpholinetetraphenylborate Also necessary In addition to the above raw materials, inorganic fillers, antimony trioxide, flame retardants such as phosphorus compounds, pigments, and coupling agents such as silane coupling agents may be used depending on the material. The inorganic filler is not particularly limited, and includes commonly used quartz glass powder, talc, and silica powder.

Alumina powder or the like is appropriately used.

The epoxy resin composition used in this invention can be produced, for example, as follows.

That is, the above (A), (B), and (C) components are appropriately blended with other additives such as pigments and coupling agents, and the mixture is kneaded in a heated state by applying a kneading machine such as a mixing roll machine. The desired epoxy resin composition can be obtained through a series of steps of melt-mixing, cooling to room temperature, pulverizing by known means, and, if necessary, tableting.

Sealing of a semiconductor element using such an epoxy resin composition is not particularly limited, and can be performed by a known molding method such as ordinary transfer molding.

The semiconductor device obtained in this way has a substance in the epoxy resin composition that relieves the internal stress generated at the filler/epoxy matrix interface, and also significantly reduces its electrical properties and moisture resistance. Since it contains no curing accelerator or only a very small amount of curing accelerator, it has extremely excellent electrical properties and low stress properties.

〔Effect of the invention〕

The semiconductor device of the present invention is encapsulated using a special epoxy resin composition containing the above-mentioned special silica filler, and containing no or significantly reduced curing accelerator. Furthermore, the sealing plastic package differs from conventional epoxy resin compositions due to the internal stress-relaxing effect of the reaction product in the sealing resin, resulting in extremely low internal stress. It has high electrical properties, high heat resistance reliability, and low internal stress, making it extremely reliable.In particular, by sealing with the above special epoxy resin composition, it can be used for 8 bottles or more, especially 16 pins or more, or This is a major feature, as it allows large semiconductor devices with chips with longer sides of 4 or more to achieve the above-mentioned high reliability.Furthermore, the silica filler contains a special binder, etc. The special ingredients used in this product are applicable to a wide range of epoxy resins, and manufacturing is simple, so there is no need to add special processes to the manufacturing of semiconductor devices, reducing the complexity of manufacturing semiconductor devices. I don't even invite you.

Next, examples will be described.

[Examples 1 to 6] First, six types of polydimethylsiloxane oligomers a to f shown in Table 1 were prepared.

(Left below) On the other hand, prepare two types of epoxy compounds shown in Table 2,
The above six types of polydimethylsiloxane oligomers a to f and the above two types of epoxy compounds are blended in the proportions shown in the same table, and heated and mixed at 60°C using 1,4-dioxane as a medium (approximately 30% solution by weight). After completion of the reaction, the mixture was dried under reduced pressure to produce reaction products 1 to 12. Next, a 30% by weight toluene solution of the above reaction product and silica were mixed at a weight ratio of 2:1, both components were allowed to react, and then filtered. After further drying under reduced pressure to scatter the solvent, 15
Coated silica whose particle surfaces are coated with the above polydimethylsiloxane oligomer by heating at 0°C for 2 hours
- got u. The amount of coverage of the reaction product of the polydimethylsiloxane oligomer and the epoxy compound on the surface of the silica particles was determined from the amount of silica remaining by extracting the reaction product with toluene from weighed silica (before heating) under reflux.

(Left below) Next, using the coated silica obtained as above,
This and the raw materials shown in Table 3 below were blended and kneaded on a mixing roll machine at 100°C for 10 minutes to obtain a sheet composition. Here, the amount of coating silica added was adjusted based on the measured value of the coating amount of the reaction product described above so that the amount of silica alone added was 700 parts by weight. The obtained C-I-shaped composition was then pulverized to obtain the desired powdered epoxy resin composition.

As a reference example, polybutadiene-acrylonitrile copolymer in which both ends of the molecular chain are carboxyl groups (manufactured by Ube Industries, Hiker CT Polymer, CTBN)
1300X8. Viscosity: 125000cps (27
℃) 4 Molecular weight: 3500. Acrylonitrile content: 17
%, carboxyl fund, l: 2.37%), and the raw materials shown in Table 3 were blended in the proportions shown in the same table to prepare a powdered epoxy resin composition. Further, as a conventional example, a powdered epoxy resin composition was prepared using the raw materials shown in Table 3 below in the proportions shown in the same table.

A semiconductor device was obtained by molding a semiconductor element by transfer molding using the powdered epoxy resin composition obtained in the above Examples, Reference Examples, and Conventional Examples.

The semiconductor device thus obtained was subjected to a 1000-hour reliability test (hereinafter referred to as "rPCBT test") using a pressure cooker under internal stress due to piezoresistance, 1 bending elastic modulus, and voltage applied (hereinafter abbreviated as "rPCBT test") at -50°C for 15 minutes to 150 hours.
Temperature cycle test of 2000 times for 15 minutes at °C (rT
CT test (abbreviated as “CT test”) was performed. The results are shown in Table 4 below. In addition, the glass transition temperature (Tg) indicated the temperature at which the peak of Tan δ of viscoelastic properties was exhibited.

(Left below) From the results in Table 4, it can be seen that the actual height measurement has lower internal stress in the plastic package than the reference height measurement and conventional height measurement, has good electrical insulation, and has good moisture resistance and heat resistance reliability. I know it's expensive.

[Examples 13 to 24] First, six types of polydimethylsiloxane oligomers a to f shown in Table 1 were prepared, and these and two types of epoxy compounds shown in Table 5 were mixed as shown in the table. and reacted in the same manner as Examples 1 to 12 to obtain 1 to 1.
An addition reaction product of 2 was prepared. Next, a toluene solution containing 30% by weight of the obtained addition reaction product and 1% by weight of peroxide (benzoyl peroxide) and silica were mixed at a weight ratio of 2:1 and reacted, and then filtered. By drying under reduced pressure, a coated silica was obtained in which the particle surface was coated with the polydimethylsiloxane oligomer. In this case, the time required to form the coating layer was shorter than in Examples 1 to 12. In other words, a heating time of 30 minutes at 150°C was sufficient.

Next, using the coated silica obtained as above,
This and the raw materials shown in Table 6 below were blended and kneaded on a mixing roll machine at 100°C for 10 minutes to obtain a sheet composition. Then, the obtained sheet-like composition was pulverized to obtain the desired powdered epoxy resin composition.

As a reference example, a butadiene-acrylonitrile copolymer in which both ends of the molecular chain are carboxyl groups (manufactured by Ube Industries, Ltd., Hiker CT Polymer, CTBN 13)
00X8. Viscosity: 125,000 cps (27°C) 11 Molecular weight: 3,500. Examples 1 to 12 using acrylonitrile content: 17%, carboxyl group content = 2°37%) and the raw materials shown in Table 6 below in the proportions shown in the same table.
A powdered epoxy resin composition was prepared in the same manner as above. Further, as a conventional example, powdered epoxy resin compositions were prepared in the same manner as Examples 1 to 12 using the raw materials shown in Table 6 below in the proportions shown in the same table.

(Left below) A semiconductor device was obtained by molding a semiconductor element by transfer molding using the powdered epoxy resin compositions obtained in the above examples, reference examples, and conventional examples.

Example 1 Regarding the semiconductor device thus obtained
- Various tests were conducted in the same manner as in 12. The results are shown in Table 7.

(The following is a margin.) From the results in Table 7, it can be seen that Examples 13 to 24 provide the same excellent effects as Examples 1 to 12.

That is, the products of Examples 13 to 24 have lower internal stress in their plastic packages, better electrical insulation, and higher moisture resistance and heat resistance reliability than those of the reference height measurement and conventional height measurement.

Claims (2)

[Claims] (1) A semiconductor device in which a semiconductor element is sealed using an epoxy resin composition containing the following components (A), (B), and (C). (A) Epoxy resin. (B) Phenol resin. (C) both ends of the molecular chain are composed of heterocyclic compound residues having at least two secondary amino groups within the molecule;
Addition reaction between a polydimethylsiloxane oligomer in which the chain portion of the molecular chain is bonded to the nitrogen of any secondary amino group of the terminal residue and a compound having at least two epoxy groups in the molecule. A silica filler whose particle surfaces are covered with a product-based coating layer. (2) Claim 1, wherein the epoxy resin composition contains the curing accelerator in a proportion of 0.5% by weight or less based on the total amount of components (A) and (B). semiconductor devices.