JP2000103974A - Thermosetting resin composition and semiconductor apparatus using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting resin composition having excellent storage stability, capable of providing a semiconductor apparatus suppressed in the formation of voids and having excellent soldering resistance by making the composition include a thermosetting resin, a curing agent and a curing promoter- containing microcapsule. SOLUTION: This composition comprises (A) a thermosetting resin (preferably an epoxy resin), (B) a curing agent (preferably a phenol resin) and (C) a curing promoter-containing microcapsule having a coated core/shell structure in which a core part composed of a curing promoter is coated with a shell part constituted of a polyurea consisting of an isocyanate compound of formula I and an isocyanate compound of formula II and formed by their mixture in the molar ratio of (formula I/formula II) of 80/20-30/70. Consequently, the composition capable of being melted and mixed, having low viscosity of the whole system, being sufficiently kneaded and accordingly comprising uniformly mixed and dispersed components is obtained and can be expected to have utility as a sealing material for a semiconductor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition in which each component is uniformly dispersed, and a highly reliable semiconductor device using the same.

[0002]

2. Description of the Related Art Generally, semiconductor devices such as transistors, ICs, and LSIs are encapsulated with an epoxy resin composition to form semiconductor devices. This type of epoxy resin composition usually contains various curing agents, inorganic fillers, and a curing accelerator together with the epoxy resin.

However, if a curing accelerator is added to the epoxy resin composition in advance, the curing reaction proceeds. Therefore, the epoxy resin composition is usually mixed with a curing accelerator immediately before use. Such an epoxy resin composition,
Store the curing accelerator separately and mix and mix as necessary.However, since the pot life after mixing is relatively short, large amounts cannot be mixed. It has to be compounded a plurality of times, and the work efficiency is extremely poor.

On the other hand, as a solution to such a problem, for example, a curing accelerator-containing microcapsule in which a curing accelerator is encapsulated in a microcapsule using an epoxy resin as a shell portion (wall film) forming material is contained. Epoxy resin compositions have been proposed (Japanese Patent Laid-Open No. 24261/1990).
No. 6). Further, as a material for forming a shell portion (wall film) of the microcapsule, in addition to the epoxy resin, various polymers such as polystyrene, polymethacrylic acid methyl ester, ethylene-vinyl acetate copolymer, polyvinyl toluene, and acrylic rubber; Various epoxy resin compositions containing microcapsules containing a curing accelerator using a polymer obtained by using an ethylene-based monomer such as vinylidene chloride, acrylonitrile, or methacrylic acid as a main monomer have been proposed.

[0005]

However, when the epoxy resin composition is produced by blending and kneading the above-mentioned various hardening agent-containing microcapsules together with other components, the kneading temperature is usually set at 100 ° C. Since the temperature was set at around ℃ (resin temperature), the viscosity of the entire system was high and sufficient kneading was not possible. Therefore, there is a problem that the obtained epoxy resin composition is inferior in dispersibility of each component. In particular, in the case of a highly filled system in which the proportion of the inorganic filler exceeds 80% by weight of the entire epoxy resin composition, the obtained epoxy resin composition has particularly poor dispersibility of the inorganic filler.
Therefore, when a semiconductor element is sealed with such an epoxy resin composition, voids are generated and a problem arises that solder resistance is poor.

Therefore, it is considered that the kneading temperature is set higher than 100 ° C. to lower the viscosity of the entire system and kneading is sufficiently performed. However, if the kneading temperature is too high, the shell portion of the hardening accelerator-containing microcapsules is increased. (Wall film) is softened or dissolved, and the contained curing accelerator is released. As a result, a curing accelerator is released into the obtained epoxy resin composition, the reaction proceeds, and a problem arises that storage stability during storage is poor. On the other hand, when the kneading temperature is lower than 100 ° C., the problem of dissolution of the shell portion (wall film) can be solved, but the viscosity of the entire system becomes high, and kneading cannot be performed more sufficiently. A problem arises that the dispersibility of each component in the epoxy resin composition is further inferior.

The present invention has been made in view of such circumstances, and a thermosetting resin composition in which each component is uniformly mixed and dispersed and has excellent storage stability, and generation of voids is suppressed.
It is an object of the present invention to provide a semiconductor device having excellent solder resistance.

[0008]

Means for Solving the Problems In order to achieve the above object, the present invention provides, as a first gist, a thermosetting resin composition containing the following components (A) to (C). A second aspect is a semiconductor device in which a semiconductor element is sealed using a thermosetting resin composition. (A) Thermosetting resin. (B) a curing agent. (C) A hardening accelerator-containing microcapsule having a core / shell structure in which a core made of a hardening accelerator is coated with a shell made of the following polyurea (a). (A) A mixture of an isocyanate compound [compound (1)] represented by the following structural formula (1) and an isocyanate compound [compound (2)] represented by the following structural formula (2) is used. Wherein the molar ratio of the compound (1) to the compound (2) [compound (1) / compound (2)] is 80/20 to 30.
/ 70 is set.

[0009]

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In order to solve the above-mentioned problems of the conventional thermosetting resin composition, the present inventors first studied mainly on a material for forming a shell portion (wall film) of a microcapsule containing a curing accelerator. Was piled up. And even when performing melt mixing at a high temperature of about 130 ° C., there is no melting, and
At the time of transfer molding (175 ° C.), research was continued to obtain a shell (wall film) forming material that easily dissolves. As a result, the isocyanate compound represented by the structural formula (1) (hereinafter referred to as “compound (1)”) and the isocyanate compound represented by the structural formula (2) (hereinafter referred to as “compound (2)”) A special polyurea (a) formed by using a mixture of isocyanate compounds set in the range of compound (1) / compound (2) = 80/20 to 30/70 in a mixing molar ratio is used for a shell portion (wall film). It was found that when used for formation, the breaking temperature of the resulting polyurea was around 150 ± 15 ° C. That is, when a special polyurea (a) formed using a mixture of the above specific isocyanate compounds is used as a shell (wall film) forming material, melt mixing at a high temperature of about 130 ° C. becomes possible. Since the viscosity of the entire system is low, it has been found that kneading is sufficiently performed, and a thermosetting resin composition in which each component, particularly an inorganic filler, is uniformly dispersed is obtained. Further, when the uniformly dispersed thermosetting resin composition is used as a semiconductor encapsulating material, it has been found that the generation of voids is suppressed and a semiconductor device having excellent solder resistance is obtained, and the present invention has been achieved. did.

[0011]

Next, embodiments of the present invention will be described in detail.

The thermosetting resin composition of the present invention can be obtained by using a thermosetting resin (component A), a curing agent (component B), and a specific microcapsule containing a curing accelerator (component C). It is usually in the form of a powder or a tablet thereof.

The thermosetting resin (component A) is not particularly limited, and includes various conventionally known thermosetting resins such as an epoxy resin and a maleimide compound, and is appropriately selected depending on the application. For example, as a semiconductor sealing material, an epoxy resin is generally used.
The epoxy resin is not particularly limited. For example, biphenyl type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, novolak bisphenol A type epoxy resin, bisphenol A type epoxy resin, dicyclopentadiene type epoxy resin Resins. Above all, it is preferable to use a biphenyl-type epoxy resin represented by the following general formula (4) because of its low viscosity and low hygroscopicity.

[0014]

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In the above formula (4), when n = 0 and R
Those having a hydrogen atom or a methyl group as _{1 to} R ₄
It is more preferable from the viewpoint of low hygroscopicity and reactivity.

The biphenyl type epoxy resin represented by the general formula (4) includes an epoxy equivalent of 150 to 350,
Those having a softening point of 50 to 150 ° C are preferred.

The curing agent (component B) used together with the thermosetting resin (component A) is not particularly limited as long as it has a curing effect on the thermosetting resin (component A). Various curing agents are used. When an epoxy resin is used as the thermosetting resin (component A), a phenol resin is generally used as a curing agent (component B). The phenolic resin is not particularly limited, and various phenolic resins that function as a curing agent for an epoxy resin are conventionally used. Above all,
A phenol aralkyl resin is preferably used, and specifically, a phenol aralkyl resin represented by the following general formula (5) is particularly preferably used.

[0018]

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In the above formula (5), the number of repetitions n is
The range of 0 to 40 is preferred, and n = 0 to particularly preferred.
The range is 30.

The phenol aralkyl resin represented by the general formula (5) has a hydroxyl equivalent of 150 to 220 and a softening point of 4
The temperature is preferably from 0 to 110 ° C, more preferably 1 hydroxyl equivalent.
50-200, softening point 50-90 ° C.

The thermosetting resin (A component) and the curing agent (B
Component) is, for example, a thermosetting resin (A component).
When an epoxy resin is used as the curing agent and a phenol resin is used as the curing agent (component B), the hydroxyl group in the phenol resin is 0.8 to 1.2 equivalents per equivalent of the epoxy group in the epoxy resin component. It is preferable to mix them. More preferred is 0.9 to 1.1 equivalents.

A specific hardening accelerator-containing microcapsule used together with the above components A and B (component C)
Is a microcapsule having a core / shell structure in which a core made of a curing accelerator is covered with a shell made of a specific polyurea (A).

The curing accelerator included in the core is not particularly limited, and a conventionally known curing accelerator can be used. In this case, those having a liquid state at normal temperature are preferred from the viewpoint of workability in preparing the microcapsules and characteristics of the obtained microcapsules. The term “liquid at room temperature” includes not only the case where the properties of the curing accelerator itself are liquid at room temperature, but also those which are solid at room temperature but are dissolved or dispersed in any organic solvent or the like to form a liquid.

Examples of the curing accelerator include amine, imidazole, phosphorus, boron, and phosphorus-boron curing accelerators. Specifically, alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, and the like, 3- (3,4-dichlorophenyl)-
3-substituted phenyl-1,1-dimethylureas such as 1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (4-chlorophenyl) -1,1-dimethylurea, 2-methyl Imidazolines such as imidazoline, 2-phenylimidazoline, 2-undecylimidazoline and 2-heptadecylimidazoline; monoaminopyridines such as 2-aminopyridine; N, N-dimethyl-N- (2
-Hydroxy-3-allyloxypropyl) amine-N '
-Amine imides such as lactoimide, ethyl phosphine, propyl phosphine, butyl phosphine, phenyl phosphine, trimethyl phosphine, triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphine / triphenyl borane complex, Organophosphorus compounds such as tetraphenylphosphonium tetraphenylborate, and diazabicycloundecene such as 1,8-diazabicyclo [5,4,0] undecene-7 and 1,4-diazabicyclo [2,2,2] octane And the like. These can be used alone or 2
Used in combination of more than one species. Among them, the above-mentioned organic phosphorus compounds are preferably used from the viewpoint of easy production of hardening accelerator-containing microcapsules (component C) and ease of handling.

The organic solvent that can be included in the shell portion (wall film) of the microcapsules (component C) containing the curing accelerator is not particularly limited as long as it is liquid at normal temperature. It is necessary to select a material that does not dissolve the shell portion (wall film). Specifically, ethyl acetate, methyl ethyl ketone, acetone, methylene chloride,
In addition to organic solvents such as xylene, toluene and tetrahydrofuran, oils such as phenylxylylethane and dialkylnaphthalene can be used.

The specific polyurea (a) forming the shell portion (wall film) is formed using a mixture of an isocyanate compound consisting of the compound (1) and the compound (2).

The above compound (1) can be prepared, for example, as follows. That is, it can be easily prepared by carrying out an addition reaction of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate in ethyl acetate.

The above compound (2) can be prepared, for example, as follows. That is, it can be easily prepared by carrying out an addition reaction of 1 mol of trimethylolpropane and 3 mol of 2,4-tolylene diisocyanate in ethyl acetate. In this case, a small amount of a tin-based catalyst may be used as the urethanization catalyst.

The molar ratio of the compound (1) to the compound (2) [compound (1) / compound (2)] is 80/20 to
It needs to be set to 30/70. Particularly preferably, the molar ratio of both (compound (1) / compound (2)) is 70/3.
The range is 0 to 50/50. That is, compound (1)
Is more than 80 (compound (2) is less than 20), the breaking start temperature of the shell becomes 135 ° C. or lower, and the kneading becomes insufficient, and in some cases, the contained catalyst acts and reacts. Conversely, if the content of the compound (1) is less than 30 (the content of the compound (2) exceeds 70), the temperature at which the shell starts to break becomes a high temperature of 165 ° C. or more, and the curing reaction at the time of molding the semiconductor element is inferior. .

The compound (1) and the compound (2)
By setting the molar ratio in the above range, the breaking temperature of the shell portion (wall film) can be set in a suitable range (150 ± 15 ° C.). For example, the compound (1)
When the molar ratio [compound (1) / compound (2)] of both the compound (2) and the compound (2) is 70/30 to 50/50, the breaking temperature of the shell part (wall film) is set to around 150 to 160 ° C. It is possible to do. Therefore, when a thermosetting resin composition is prepared by blending the components A to C, melt mixing at a high temperature of about 130 ° C., which has been conventionally difficult, becomes possible.
The viscosity of the entire system is low, and the shearing force is also small, and as a result of sufficient kneading, the obtained thermosetting resin composition is
Each component, particularly an inorganic filler, is uniformly mixed and dispersed.

The polyurea (a) formed by a mixture of the isocyanate compound consisting of the compound (1) and the compound (2) includes a repeating unit represented by the following general formula (3) as a main component. Is preferred.

[0032]

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As described above, in equation (3), R ₁ ,
R ₂ is a hydrogen atom or a monovalent organic group;
Is preferably a divalent organic group, particularly preferably R ₁ , R
₂ is the case where both are hydrogen atoms.

The specific polyurea (a) having the repeating unit represented by the general formula (3) as a main component is generally prepared by mixing a mixture of the isocyanate compound comprising the compound (1) and the compound (2) with: Obtained by reaction with water. That is, an amine is formed by hydrolysis of a mixture of an isocyanate compound composed of the compound (1) and the compound (2), and the amine is formed by reacting with an unreacted isocyanate group (so-called self-polyaddition reaction). The production of the above specific polyurea (a)
It is not limited to such a self-polyaddition reaction,
For example, it can also be obtained by a polyaddition reaction of a mixture of an isocyanate compound composed of the compound (1) and the compound (2) with a polyvalent amine.

The above polyvalent amines may be compounds having two or more amino groups in the molecule, and specifically include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,6-hexamethylenediamine. 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, o-phenylenediamine, m-
Phenylenediamine, p-phenylenediamine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, menthanediamine, bis (4-amino-3-methylcyclohexyl) methane, isophoronediamine, 1,3-diamino Cyclohexane, spiro acetal type diamine and the like can be mentioned. These may be used alone or in combination of two or more. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferred from the viewpoint of the isolation ability (protection ability) of the formed microcapsule wall membrane.

The curing accelerator-containing microcapsules (C
Component) is not particularly limited as long as it can be microencapsulated, and can be prepared by various conventionally known methods. In particular, it is preferable to form a shell portion (wall film) by using an interfacial polymerization method and microencapsulate the shell portion (wall film) from the viewpoint of homogenizing the shell portion (wall film) and adjusting the thickness of the wall film.

The microcapsules (component C) containing a curing accelerator obtained by the above interfacial polymerization method are obtained, for example, as follows. That is, a mixture of an isocyanate compound comprising a compound (1) and a compound (2) is dissolved in a liquid curing accelerator as a core component. The solution obtained in this way is oily, and this is dispersed in the water phase as an oil phase in the form of oil droplets to produce an O / W type (oil phase / water phase type) emulsion. At this time, the particle diameter of each dispersed oil droplet is 0.05 to 50 μm, preferably 0.05 to 20 μm.
It is preferable from the viewpoint of the stability of the emulsion during polymerization.

On the other hand, when a solid curing accelerator is dissolved in an organic solvent to form a core component, an emulsion of S / O / W (solid phase / oil phase / water phase) type is obtained. Also, this emulsion type is when the curing accelerator is lipophilic,
When the curing accelerator has hydrophilicity, it is difficult to form the emulsion type, but in this case, the solubility is adjusted so that an O / O (oil phase / oil phase) emulsion type or S / O Interfacial polymerization may be performed as a / O (solid phase / oil phase / oil phase) emulsion type.

Next, a polyamine or a polyhydric alcohol is added to the aqueous phase of the emulsion to cause interfacial polymerization with the mixed isocyanate compound in the oil phase to carry out a polyaddition reaction, whereby the specific polyurea ( A hardening accelerator-containing microcapsule (component C) having (a) as a shell portion (wall film) is obtained.

The hardening accelerator-containing microcapsules (component C) thus obtained have a core / shell structure, and the shell (wall film) contains the hardening accelerator as a core component. Things. The curing accelerator-containing microcapsules (component C) can be isolated by a conventionally known means, for example, a method of drying after centrifugation or a means of spray drying. Further, it can be dissolved and mixed in the thermosetting resin or the curing agent. At this time, if necessary, the organic solvent in the microcapsules can be removed by using a means such as drying under reduced pressure.

This curing accelerator-containing microcapsule (C
The average particle size of the component (A) is 0.05 to 20 in consideration of the shearing force applied during the production of the thermosetting resin composition, as described later.
It is preferable to set it in the range of μm, preferably in the range of 0.1 to 4 μm from the viewpoint of the stability and dispersibility of the microcapsules. In the present invention, the shape of the curing accelerator-containing microcapsules (component C) is preferably spherical, but may be elliptical. If the microcapsules are not spherical in shape but have a uniform particle size, such as elliptical or flat, the simple average value of the longest and shortest diameters is defined as the average particle size.

This curing accelerator-containing microcapsule (C
In the component), the amount of the included curing accelerator is preferably set to 5 to 70% by weight, particularly preferably 10 to 50% by weight, based on the total amount of the microcapsules. That is, when the encapsulation amount of the curing accelerator is less than 5% by weight, the curing reaction time is too long, and the reactivity becomes poor. Conversely, when the encapsulation amount of the curing accelerator exceeds 70% by weight, the shell portion (wall film) is formed. ) Is too thin, and there is a possibility that the encapsulated curing accelerator (core component) may have poor isolation and mechanical strength.

The ratio of the thickness of the shell portion (wall film) to the particle size of the hardening agent-containing microcapsules (component C) is preferably set to 3 to 25%, particularly preferably 5 to 25%. Is set. That is, if the above ratio is less than 3%, sufficient mechanical strength cannot be obtained with respect to the shearing force (shear) applied in the kneading step in the production of the thermosetting resin composition, and if it exceeds 25%, it is included. This is because the release of the curing accelerator tends to be insufficient.

When the epoxy resin is used as the thermosetting resin (component A), the curing accelerator-containing microcapsules (component C) are mixed in an amount of 100 parts by weight of epoxy resin (hereinafter, "parts"). 0.1 to 3)
It is preferable to set to 0 part. Particularly preferably, 7 to 2
0 parts. That is, if the amount of the curing accelerator-containing microcapsules (component C) is less than 0.1 part, the curing speed is too slow to cause a decrease in strength, and if it exceeds 30 parts, the curing speed is too fast. Liquidity is impaired.

Further, the thermosetting resin composition of the present invention includes:
Depending on the use, an inorganic filler can be appropriately compounded together with the above-mentioned components A to C. Examples of the inorganic filler include silica, clay, gypsum, calcium carbonate, barium sulfate, alumina oxide, beryllium oxide, silicon carbide, silicon nitride and the like. Among them, silica, particularly fused silica, is preferably used.

The amount of the inorganic filler is preferably set to 70 to 95% by weight of the whole thermosetting resin composition. Particularly preferably, it is 80 to 95% by weight.

The thermosetting resin composition of the present invention includes:
In addition to the above-described components A to C and the inorganic filler, other additives can be appropriately compounded as needed.

Examples of the other additives include a flame retardant and a wax.

Examples of the flame retardant include novolak type brominated epoxy resin, brominated bisphenol A type epoxy resin, antimony trioxide, antimony pentoxide, and the like. These may be used alone or in combination of two or more.

Examples of the wax include compounds such as higher fatty acids, higher fatty acid esters, and higher fatty acid calcium, and they can be used alone or in combination of two or more.

Further, the thermosetting resin composition of the present invention may contain components such as silicone oil, silicone rubber, synthetic rubber, etc., in addition to the above-mentioned other additives, to reduce stress, and to provide a moisture resistance reliability test. An ion trapping agent such as hydrotalcites and bismuth hydroxide may be blended for the purpose of improving the reliability in the above.

The thermosetting resin composition of the present invention is, for example,
It can be manufactured as follows. First, as described above, a curing accelerator-containing microcapsule (C component) is prepared by an interfacial polymerization method.

Then, after mixing all the remaining components together with the hardening accelerator-containing microcapsules (component C), the mixture is kneaded in a kneading machine such as a mixing roll machine in a heated state and melted and mixed. The temperature setting during kneading can be set higher than before. And then,
Although heat and shear force act on the hardening accelerator-containing microcapsules (component C), the thermal stability is good at this stage because the breaking temperature of the shell portion (wall film) of the microcapsules is higher than before. The kneading temperature is high and the shearing force applied to the microcapsules can be reduced. In this microcapsule,
A specific polyurea (a) having a property that the shell portion (wall film) is easily broken by heat during resin encapsulation molding using a thermosetting resin composition is used as a shell portion (wall film) forming material. I have. Further, with respect to the shearing force applied to the microcapsules, the average particle size of the microcapsules is set to 0.05.
It is preferable to set the thickness in the range of 20 to 20 μm, preferably 0.1 to 4 μm from the viewpoint of the stability and dispersibility of the microcapsules.

Next, after cooling at room temperature, the mixture is pulverized by a known means and, if necessary, tableted to produce a desired thermosetting resin composition through a series of steps. be able to.

In the present invention, the sealing of the semiconductor element using the above-mentioned thermosetting resin composition is not particularly limited, and can be performed by a known molding method such as ordinary transfer molding.

The semiconductor device thus obtained contains a hardening accelerator having a core / shell structure in which a core made of a hardening accelerator is covered with a shell portion (wall film) made of a specific polyurea (a). Since the resin is sealed with the thermosetting resin composition using the microcapsules (C component), the generation of voids is suppressed by the resin sealing with the thermosetting resin composition in which each component is uniformly dispersed. Thus, a semiconductor package having excellent solder resistance can be obtained.

Next, examples will be described together with comparative examples.

Prior to the examples, hardening accelerator-containing microcapsules were prepared according to the following method.

[Microcapsules C1 containing a curing accelerator]
It was produced by the above-mentioned interfacial polymerization method. That is, in more detail, 10.5 parts of the compound (1) and 6.6 parts of the compound (2) are uniformly mixed with 6.7 parts of triphenylphosphine and 4.8 parts of ethyl acetate which are curing accelerators. To prepare an oil phase. The molar ratio of the compound (1) to the compound (2) is [compound (1) / compound (2)] = 6/4. Further, an aqueous phase composed of 95 parts of distilled water and 5 parts of polyvinyl alcohol was separately prepared, and the oil phase prepared above was added thereto, and a homomixer (800 parts) was added.
The mixture was emulsified at 0 rpm) to form an emulsion, which was charged into a polymerization reactor equipped with a reflux tube, a stirrer, and a dropping funnel.

On the other hand, 13 parts of an aqueous solution containing 3 parts of triethylenetetramine was prepared, placed in a dropping funnel provided in the polymerization reactor, dropped into the emulsion in the reactor, and polymerized at 70 ° C. for 3 hours. Then, microcapsules were produced. The polyurea shell containing triphenylphosphine as described above (shell thickness ratio to particle size of 20)
%) Structured microcapsules (average particle size 2μ)
m, breaking temperature of shell part 150 ° C).

[Hardening Accelerator-Containing Microcapsules C2]
The molar ratio of the compound (1) to the compound (2) was set to [compound (1) / compound (2)] = 7/3. Except for that, microcapsules containing a hardening accelerator were produced in the same manner as in Example 1 (average particle size: 2 μm, breaking temperature of shell portion: 140 ° C.).

[Microcapsules C3 containing a curing accelerator]
The molar ratio between the compound (1) and the compound (2) was set to [compound (1) / compound (2)] = 1/9. Except for this, a curing accelerator-containing microcapsule was produced in the same manner as in Example 1 (average particle diameter: 2 μm, shell part breaking temperature: 175 ° C.).

[Hardening Accelerator-Containing Microcapsules C4]
The molar ratio of the compound (1) to the compound (2) was set to [compound (1) / compound (2)] = 9/1. Except for this, a curing accelerator-containing microcapsule was produced in the same manner as in Example 1 (average particle size: 2 μm, breaking temperature of shell portion: 120 ° C.).

[Microcapsule C5 containing a curing accelerator]
The molar ratio of the compound (1) and the compound (2) was set to [compound (1) / compound (2)] = 2/8. Except for this, a curing accelerator-containing microcapsule was produced in the same manner as in Example 1 (average particle size: 2 μm, breaking temperature of shell portion: 170 ° C.).

[Microcapsules C6 containing a curing accelerator]
The molar ratio of the compound (1) to the compound (2) was set to [compound (1) / compound (2)] = 3/7. Except for this, a curing accelerator-containing microcapsule was produced in the same manner as in Example 1 (average particle size: 2 μm, breaking temperature of shell portion: 165 ° C.).

[Hardening Accelerator-Containing Microcapsules C7]
The molar ratio of the compound (1) to the compound (2) was set to [compound (1) / compound (2)] = 8/2. Except for this, a curing accelerator-containing microcapsule was produced in the same manner as in Example 1 (average particle size: 2 μm, breaking temperature of shell portion: 135 ° C.).

On the other hand, the following components were prepared.

[Thermosetting resin A1] 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'
-Tetramethylbiphenyl

[Thermosetting resin A2] Cresol novolak type epoxy resin (epoxy equivalent 198)

[Curing agent B1] A phenol aralkyl resin represented by the above general formula (5) (hydroxyl equivalent: 175: n = 0 to 21 in the formula (5))

[Hardener B2] Phenol novolak resin (hydroxyl equivalent 105)

[Inorganic filler] Fragmented fused silica having an average particle size of 15 μm

[Brominated epoxy resin] Epoxy equivalent 2
75% bromide content at 75%

[0074]

Examples 1 to 7 and Comparative Examples 1 to 4 Tables 1 and 2 below
Were mixed in the proportions shown in the same table, kneaded with a mixing roll machine, cooled, and then pulverized to obtain a desired powdery thermosetting resin composition. The kneading temperatures are shown in Tables 1 and 2 below.

[0075]

[Table 1]

[0076]

[Table 2]

Using the thus obtained powdery thermosetting resin compositions of Examples and Comparative Examples, the following evaluation tests (gel time at 175 ° C., 6 times at 175 ° C.)
Hardness after 0 second, storage stability). The results are shown in Tables 3 and 4 below.

[Gel time at 175 ° C.] 175 ° C.
Was measured according to a hot plate gel time.

[Hardness after 60 seconds at 175 ° C.] 175 ° C. ×
Immediately after molding under the condition of 60 seconds, the hardness during heating was measured using a Shore D hardness meter.

[Preservability] First, the powdery thermosetting resin composition was tablet-shaped (diameter: 24.5 mm × thickness: 20 mm).
Preformed. Pre-set the tablet at the specified temperature (17
(5 ± 5 ° C), and insert it into the spiral spiral mold for the spiral flow until it reaches the end.
It was increased to 0 ± 10 kg / cm ² . Next, when the mold clamping pressure reached 210 ± 10 kg / cm ² , the thermosetting resin composition was injected with a plunger, and the injection pressure was set to 70 ± 5.
After reaching kg / cm ² , injection pressure was applied for 1 minute and 50 seconds. Next, the plunger pressure of the transfer molding machine was released, and the mold clamping pressure was released to open the mold. The spiral flow value was obtained by measuring the spiral length of the molded product to a minimum of 2.5 mm (EMMI 1-6).
6). This was defined as the initial spiral flow value (initial SF value).

On the other hand, in the same manner as described above, the powdery thermosetting resin composition was tableted (diameter: 24.5 mm × thickness: 20 mm).
mm), and the tablet was left at a temperature of 30 ° C. for 3 days. Using this tablet after leaving,
A spiral flow value was obtained in the same manner as in the measurement of the initial SF value. This was defined as a spiral flow value after storage for 3 days (SF value after storage).

The spiral flow retention (%) was calculated from the above initial SF value and stored SF value by the following equation.

[0083]

## EQU1 ## Spiral flow retention (%) = (SF after storage)
Value) / (initial SF value) × 100

[Releaseability] First, using a mold having a three-layer structure (upper mold 10, middle mold 11, lower mold 12) as shown in FIG. 1, molding was performed at 175 ° C. for 60 seconds. The load at the time of mold release in the cured epoxy resin composition was measured. In the figure, 13 is a cull, 14 is a sprue, 15 is a runner, and 16 is a cavity. As shown in FIG. 2, the measurement of the load at the time of releasing the mold is performed by moving the middle mold 11 of the molding
The epoxy resin composition cured body 19 in the middle mold 11 was removed from above from above using a push-pull gauge 18. The load value at this time was measured.

Further, the powdery thermosetting resin compositions obtained in the above Examples and Comparative Examples were preformed into tablets (diameter: 24.5 mm × thickness: 20 mm). It was left under temperature conditions for 3 days. Then, the semiconductor device [8]
0-pin 4-way flat package: QFP-80 (14
mm x 20 mm x 2.7 mm thickness), lead frame M
F202, semiconductor element (8 mm × 8 mm × thickness 0.37
mm)] by transfer molding (conditions: 175 ° C. × 2
Min).

[Evaluation of Molding Failure] First, the number of molding failures (out of 120) of the obtained semiconductor devices was measured. That is, an automatic molding machine (manufactured by TOWA, VP
In S-40), use the above QFP-80 (14 mm x 20 mm x
(2.7 mm thick) were molded in 10 shots, and the occurrence of unfilling and the formation of voids were evaluated. The formation of the above voids was measured by a soft X-ray apparatus, and those having a diameter of 0.1 mm or more were determined to be defective. Further, the obtained semiconductor device was subjected to a condition of 121 ° C. × 2 atm × 100% RH (PCT test), and a conduction test of a test device in the package was performed.

[Solder Crack Resistance] Using the obtained semiconductor device, after pre-baking at 120 ° C. × 1 hour, and then absorbing the moisture at 85 ° C./85% RH × 168 hours, the Vapor Phase at 215 ° C. Solder
ing (VPS) 90 seconds evaluation test (crack resistance)
Was done. The results are shown in Tables 3 and 4 below.

[0088]

[Table 3]

[0089]

[Table 4]

From the results shown in Tables 3 and 4, it can be seen that all the products of Examples have a high spiral flow retention rate and excellent storage stability. In addition, since the molded article has excellent releasability and a molded article failure rate of 0%, the thermosetting resin composition of the example has high storage stability, and is used as a sealing material for semiconductor devices. It turns out that it is suitable for use. Further, good results were obtained in the PCT test and the crack resistance test. For this reason, when the thermosetting resin composition of the example is used as a sealing material for a semiconductor device, generation of voids is suppressed and a highly reliable semiconductor device can be obtained. On the other hand, the products of Comparative Examples 1 and 4 have a high spiral flow retention rate, but have a low hot hardness of the molded product and have a high PCT.
The test and crack resistance test results were poor. Also,
Comparative Examples 2 and 3 had low spiral flow retention, and PC
The results of the T test and the crack resistance test were also poor.

[0091]

As described above, the thermosetting resin composition of the present invention comprises a thermosetting resin (A component) and a curing agent (B component).
And specific hardening accelerator-containing microcapsules (component C)
Is obtained by using As the material for forming the shell portion (wall film) of the specific curing accelerator-containing microcapsule (component C), the specific polyurea (a) is used.
Is used, the breaking temperature of the shell portion (wall film) to be formed is about 150 ± 15 ° C., and melt mixing at a high temperature of about 130 ° C. becomes possible. As a result, the viscosity of the entire system is reduced and kneading is sufficiently performed, so that a thermosetting resin composition in which each component is uniformly mixed and dispersed can be obtained. In particular, even if the proportion of the inorganic filler is a high-filling type in which the proportion of the inorganic filler exceeds 80% by weight of the entire thermosetting resin composition, a thermosetting resin composition in which the inorganic filler is uniformly mixed and dispersed is obtained. be able to.

When a thermosetting resin composition in which the above components are uniformly mixed and dispersed is used as a semiconductor encapsulating material, the generation of voids is suppressed and a semiconductor device having excellent solder resistance is obtained. be able to. Further, the thermosetting resin composition of the present invention is most suitable as a sealing material for a semiconductor device as described above, but is also useful in other fields, for example, fields such as adhesion and paint.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a method for molding a cured epoxy resin composition used in a method for evaluating mold release properties.

FIG. 2 is an explanatory view showing a method for measuring a load, which is a method for evaluating releasability.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Kazuhiro Ikemura 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Tadaaki Harada 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Inside Nitto Denko Corporation (72) Inventor Sadahito Misumi 1-1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Inside Nitto Denko Corporation (72) Takeshi Taniguchi 1-1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Inside (72) Inventor Shinichi Oizumi 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Minoru Yamane 1-2-1, Shimohozumi, Ibaraki-shi, Osaka Nitto Denko stock In company

Claims (6)

[Claims] 1. A thermosetting resin composition comprising the following components (A) to (C). (A) Thermosetting resin. (B) a curing agent. (C) A hardening accelerator-containing microcapsule having a core / shell structure in which a core made of a hardening accelerator is coated with a shell made of the following polyurea (a). (A) A mixture of an isocyanate compound [compound (1)] represented by the following structural formula (1) and an isocyanate compound [compound (2)] represented by the following structural formula (2) is used. Wherein the molar ratio of the compound (1) to the compound (2) [compound (1) / compound (2)] is 80/20 to 30.
/ 70 is set. Embedded image Embedded image 2. The thermosetting resin composition according to claim 1, wherein the thermosetting resin as the component (A) is an epoxy resin, and the curing agent as the component (B) is a phenol resin. 3. The thermosetting resin composition according to claim 2, wherein said epoxy resin is a biphenyl type epoxy resin. 4. The thermosetting resin composition according to claim 2, wherein the phenol resin is a phenol aralkyl resin. 5. The polyurea (a) constituting the shell portion comprises a repeating unit represented by the following general formula (3) as a main component. The thermosetting resin composition according to the above. Embedded image 6. A semiconductor device comprising a semiconductor element encapsulated with the thermosetting resin composition according to claim 1.