JP2000309681A - Resin composition for semiconductor sealing use and semiconductor device using the same, and production of the semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in moisture resistance reliability, storage stability, ejecting operability and coating operability by making the composition include a liquid epoxy resin, solid phenolic resin, latent curing promoter, etc., and setting the viscosity of the composition to be at specified levels at specific temperatures, respectively. SOLUTION: This composition is obtained by being made to include (A) a liquid epoxy resin such as bisphenol F-type epoxy resin, (B) a solid phenolic resin, pref. polyfunctional solid phenolic resin, (C) a latent curing promoter, and (D) an inorganic filler, pref. spherical fused silica powder, and setting the viscosity of the composition at >=7,000 p at 25 deg.C and <=5,000 p at 80 deg.C, wherein the component C is pref. a microencapsulated type curing promoter having core/shell structure where a core portion consisting of a curing promoter such as triphenylphsphine is coated with a shell portion consisting mainly of a polymer composed of structural unit of the formula (R is a bivalent or trivalent organic group; R1 and R2 are each H or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin-based sealant, which exhibits a low viscosity at a relatively low temperature of 80.degree. C. or lower, and is particularly excellent in discharge and coating workability and storage stability. The present invention relates to a resin composition for semiconductor encapsulation, a semiconductor device using the same, and a method for manufacturing a semiconductor device.

[0002]

2. Description of the Related Art Conventionally, TAB (Tape Automated Bon
ding, tape automated bonding), COB
Liquid sealants are used for semiconductor sealing in (Chip On Board, chip on board) and the like. The liquid sealing agent is used at room temperature (25 ° C.), and the semiconductor element is sealed with a dispenser, printing, or the like, thereby manufacturing a semiconductor device. As such a liquid sealing agent, an epoxy resin composition containing a liquid epoxy resin, an acid anhydride-based curing agent, a usual curing accelerator, and silica powder is generally known. .

[0003]

However, since the above-mentioned liquid sealant uses an acid anhydride-based curing agent as a curing agent, liquefaction of the sealant is easy, and discharge and coating workability is good. However, there is a problem that the moisture absorption rate under moisture resistance is high and the humidity resistance reliability is poor. In addition, the liquid sealant is poor in storage stability because it is liquid at room temperature, the viscosity is greatly increased during storage at room temperature, or silica powder is settled, and the resin is frozen and solidified. , It is necessary to take special storage measures.

The present invention has been made in view of such circumstances, and uses a resin composition for semiconductor encapsulation which has excellent moisture resistance reliability and storage stability, and also has excellent discharge and coating workability. It is an object to provide a semiconductor device and a method for manufacturing the semiconductor device.

[0005]

In order to achieve the above object, the present invention provides a resin composition for encapsulating a semiconductor, comprising the following components (A) to (D): The first gist is a resin composition for semiconductor encapsulation in which the viscosity of the resin composition is set to 7000 poise or more at 25 ° C. and 5000 poise or less at 80 ° C. (A) Liquid epoxy resin. (B) Solid phenolic resin. (C) Latent curing accelerator. (D) an inorganic filler.

Further, according to the present invention, a semiconductor element is mounted on a printed circuit board via a plurality of connection electrodes, and a gap between the printed circuit board and the semiconductor element is sealed by a sealing resin layer. A second subject matter of the present invention is a semiconductor device, wherein the sealing resin layer is formed of the semiconductor sealing resin composition.

Further, according to the present invention, a semiconductor element is mounted on a printed circuit board via a plurality of connection electrodes, and a gap between the printed circuit board and the semiconductor element is sealed by a sealing resin layer. A method of manufacturing a semiconductor device comprising: filling a gap between the printed circuit board and a semiconductor element with the resin composition for semiconductor encapsulation; and curing the resin composition to form the sealing resin layer. A third aspect of the present invention is a method of manufacturing a semiconductor device.

A semiconductor element is mounted on the surface of the printed circuit board, the printed circuit board is electrically connected to the semiconductor element, and the periphery of the semiconductor element is sealed by a sealing resin layer so as to incorporate the semiconductor element. A fourth aspect of the present invention is a semiconductor device in which the sealing resin layer is formed of the semiconductor sealing resin composition.

Further, the semiconductor element is mounted on the surface of the printed circuit board, the printed circuit board is electrically connected to the semiconductor element, and the periphery of the semiconductor element is sealed with a sealing resin layer so as to incorporate the semiconductor element. A method of manufacturing a semiconductor device, comprising: supplying the semiconductor sealing resin composition onto a wiring circuit board on the semiconductor element mounting surface side, and then curing the semiconductor composition to form the sealing resin layer. The manufacturing method of the device is the fifth gist.

Then, a semiconductor device having a resin sealing layer formed on a mounting substrate via a plurality of connection electrode portions is mounted with its own wiring circuit board facing the semiconductor device. A semiconductor product having a gap between a substrate and a semiconductor device sealed with a sealing resin layer, wherein the sealing resin layer is formed of the semiconductor sealing resin composition. The gist of 6.

That is, the present inventors have conducted a series of studies to obtain a sealing material which is excellent in moisture resistance reliability and storage stability and also excellent in discharge and coating workability. As a result, when a liquid epoxy resin, a solid phenol resin, a latent curing accelerator, and an inorganic filler are used, and a resin composition having a specific viscosity at each of 25 ° C. and 80 ° C. is used, Have been achieved, and the present invention has been achieved.

In particular, when a polyfunctional solid phenol resin is used as the solid phenol resin, there is an advantage that the glass transition temperature (Tg) is increased and the heat resistance is improved.

In the case where a microcapsule-type curing accelerator having a core / shell structure in which a core composed of a curing accelerator is coated in a specific shell portion is used as the latent curing accelerator. The semiconductor encapsulating resin composition has the advantage that the pot life is extremely long and the storage stability is particularly excellent.

Further, when spherical fused silica powder is used as the inorganic filler and is contained in a specific ratio in the whole resin composition for semiconductor encapsulation, the fluidity becomes excellent and the discharge and coating are performed. There is an advantage that workability is particularly excellent.

[0015]

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

The resin composition for encapsulating a semiconductor of the present invention comprises a liquid epoxy resin (component A), a solid phenol resin (component B), a latent curing accelerator (component C), and an inorganic filler (component D). ) And has a specific viscosity at each of 25 ° C. and 80 ° C.

The liquid epoxy resin (component A) is not particularly limited as long as it is liquid at 25 ° C., and various epoxy resins can be used. For example, bisphenol F type epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, allylated bisphenol type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more. In the present invention, the liquid epoxy resin, when used alone, shows a liquid state at 25 ° C., and when two or more kinds are used in combination, the epoxy resin component finally becomes 25 ° C.
It is intended to include those that show liquid.

As the liquid epoxy resin which is the component A, it is preferable to use one having an epoxy equivalent of 110 to 220 g / ep.
It is preferable to use one having 0 to 200 g / ep.

The solid phenolic resin (component (B)) used together with the component (A) serves as a curing agent for the liquid epoxy resin (component (A)).
It is not particularly limited as long as it shows a solid at ℃, and various phenol resins can be used, but tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrohydrochloride can be used as long as the initial purpose is not impaired. Acid anhydride-based curing agents such as phthalic anhydride and phthalic anhydride and amines may be used in combination. Examples of the solid phenol resin include a polyfunctional solid phenol resin, a bisphenol resin, a naphthalene-type phenol resin, a phenol novolak resin, and a triphenylmethane-type phenol resin. These may be used alone or in combination of two or more. Here, the polyfunctional solid phenol resin is
It has at least one aromatic ring having two or more phenolic hydroxyl groups, and the total number of phenolic hydroxyl groups in one molecule is three or more, and has at least two aromatic rings in one molecule. Refers to solid phenolic resin. As such a polyfunctional solid phenol resin, for example, trifunctional solid phenol resin, tetrafunctional solid phenol resin,
Examples include pentafunctional solid phenolic resins. When a polyfunctional solid phenol resin is used, it is preferable to use one having a number average molecular weight of 450 or less. In the present invention, the solid phenolic resin, when used alone, shows a solid at 25 ° C., and when two or more kinds are used in combination, finally shows a solid at 25 ° C. as a phenol resin component. The purpose is to include.

The trifunctional solid phenol resin of the above solid phenol resin (component B) includes, for example, a phenol resin having a structure represented by the following general formula (2) and a structure represented by the following general formula (3): Phenolic resin and the like.

[0021]

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[0022]

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The above solid phenolic resin (component B)
Among them, examples of the tetrafunctional solid phenol resin include a phenol resin having a structure represented by the following general formula (4) and a phenol resin having a structure represented by the following general formula (5).

[0024]

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[0025]

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The above solid phenolic resin (component B)
Among them, examples of the pentafunctional solid phenol resin include a phenol resin having a structure represented by the following general formula (6).

[0027]

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As the solid phenolic resin as the component B, those having a hydroxyl equivalent of 30 to 260 g / ep and a softening point of 40 to 100 ° C. or a melting point of 50 to 210 ° C. are preferable. Equivalent to 50 ~
It is preferable to use those having a softening point of 60 to 90 ° C. or a melting point of 70 to 190 ° C. at 110 g / ep.

The mixing ratio of the liquid epoxy resin (component A) to the solid phenol resin (component B) is such that the hydroxyl group in the phenol resin is 0.6 to 1.4 equivalents per equivalent of epoxy group in the epoxy resin. It is preferable to mix them in such a manner. More preferably, it is 0.7 to 1.1 equivalent.

In the combination of the liquid epoxy resin (component A) and the solid phenolic resin (component B), for example, it is preferable to use a combination of a bisphenol F type epoxy resin and a polyfunctional solid phenolic resin,
It is preferable from the viewpoint of heat resistance and curability.

The latent curing accelerator (component C) used together with the above-mentioned component A and component B is used for measuring the viscosity (measurement temperature) of the resin composition for semiconductor encapsulation containing the same after being left in a 50 ° C. atmosphere for 72 hours. : 80 ° C.) becomes 10 times or less the viscosity before standing. For example, a polymer in which a core portion composed of various curing accelerators has a structural unit represented by the following general formula (1) A microcapsule-type curing accelerator having a core / shell structure covered with a shell portion containing as a main component, and having a reactive amino group present in the shell portion blocked. By using such a microcapsule-type curing accelerator, the resin composition for semiconductor encapsulation containing the same has an extremely long pot life and particularly excellent storage stability. Even when the amount of the ordinary curing accelerator is reduced, if the viscosity is 10 times or less, usually 1 to 3 times the viscosity before standing, it is considered as a latent curing accelerator.

[0032]

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In the microcapsule type hardening accelerator, the hardening accelerator included as the core is not particularly limited as long as it has a function of accelerating the hardening reaction, and conventionally known hardening accelerators are used. . And
In this case, those which are liquid at room temperature are preferable from the viewpoint of workability in preparing the microcapsules and characteristics of the obtained microcapsules. In addition, the liquid at room temperature means that the property of the curing accelerator itself is liquid at room temperature (25 ° C.), and that the liquid is dissolved or dispersed in any organic solvent or the like even if it is solid at room temperature. Is also included.

Examples of the included curing accelerator include amine, imidazole, phosphorus, boron, and phosphorus-boron curing accelerators. Specifically, ethyl guanidine, trimethyl guanidine,
Alkyl-substituted guanidines such as phenylguanidine and diphenylguanidine, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-
Dimethyl urea, 3- (4-chlorophenyl) -1,1-
3-substituted phenyl-1,1-dimethylureas such as dimethylurea, imidazolines such as 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, and mono-aminopyridines and the like Aminopyridines, N, N-dimethyl-N-
(2-hydroxy-3-allyloxypropyl) amine-
Amine imides such as N'-lactide, ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane Complexes, organophosphorus compounds such as tetraphenylphosphonium tetraphenylborate, diazabicycloalkenes such as 1,8-diazabicyclo [5,4,0] undecene-7,1,4-diazabicyclo [2,2,2] octane And the like. These may be used alone or in combination of two or more. Above all, the imidazole-based compound and the organic phosphorus-based compound are preferably used from the viewpoint of easy production of the hardening agent-containing microcapsules and ease of handling.

The polymer containing a polymer having the structural unit represented by the formula (1) as a main component is obtained, for example, by a polyaddition reaction between a polyvalent isocyanate and a polyvalent amine. Alternatively, it is obtained by reacting a polyvalent isocyanate with water.

The polyvalent isocyanate may be any compound having two or more isocyanate groups in the molecule. Specific examples thereof include m-phenylene diisocyanate, p-phenylene diisocyanate, and 2,4-tolylene diisocyanate. 2,6-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, 4,4'-diphenylpropane diisocyanate,
Trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate,
Butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-
Diisocyanates such as 1,4-diisocyanate, p
Phenylenediisothiocyanate, xylylene-1,
Triisocyanates such as 4-diisothiocyanate and ethylidene diisothiocyanate; tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate; hexamethylene diisocyanate and hexanetriol; Addenda,
Adducts of 2,4-tolylene diisocyanate with prenz catechol, adducts of tolylene diisocyanate and hexanetriol, adducts of tolylene diisocyanate and trimethylolpropane, adducts of xylylene diisocyanate and trimethylolpropane, hexa Like adducts of methylene diisocyanate and trimethylolpropane, trimers of aliphatic polyvalent isocyanates such as triphenyldimethylenetriisocyanate, tetraphenyltrimethylenetetraisocyanate, pentaphenyltetramethylenepentaisocyanate, lysine isocyanate, and hexamethylene diisocyanate. And isocyanate prepolymers. These may be used alone or in combination of two or more.

Among the above polyvalent isocyanates, adducts of tolylene diisocyanate and trimethylolpropane and adducts of xylylene diisocyanate and trimethylolpropane are preferable from the viewpoint of film forming property and mechanical strength when preparing microcapsules. It is preferable to use an isocyanate prepolymer represented by polymethylene polyphenyl isocyanate such as triphenyl dimethylene triisocyanate.

On the other hand, the polyamines to be reacted with the polyvalent isocyanates may be compounds having two or more amino groups in the molecule, and specifically, diethylenetriamine, triethylenetetramine, tetraethylenepentamine. Min, 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
-Diaminocyclohexane, spiroacetal diamine and the like. These may be used alone or in combination of two or more.

In the reaction between the polyvalent isocyanate and water, first, an amine is formed by hydrolysis of the polyvalent isocyanate, and this amine reacts with an unreacted isocyanate group (so-called self-polyaddition reaction). Thereby, a polymer mainly composed of the polymer having the structural unit represented by the general formula (1) is formed.

Further, as the polymer forming the shell part (wall film), for example, a polyurethane-polyurea having a urethane bond by using a polyhydric alcohol in combination with the polyvalent isocyanate can also be mentioned.

The polyhydric alcohol may be any of aliphatic, aromatic and alicyclic, such as catechol, resorcinol and 1,2-dihydroxy-4.
-Methylbenzene, 1,3-dihydroxy-5-methylbenzene, 3,4-dihydroxy-1-methylbenzene, 3,5-dihydroxy-1-methylbenzene, 2,
4-dihydroxyethylbenzene, 1,3-naphthalene diol, 1,5-naphthalene diol, 2,7-naphthalene diol, 2,3-naphthalene diol, o,
o'-biphenol, p, p'-biphenol, bisphenol A, bis- (2-hydroxyphenyl) methane, xylylene diol, ethylene glycol, 1,3
-Propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,1,1-trimethylolpropane, hexane Triol, pentaerythritol, glycerin, sorbitol and the like can be mentioned. These can be used alone or 2
Used in combination of more than one species.

The above-mentioned microcapsule-type curing accelerator can be produced, for example, through the following three steps.

[First Step] A hardening accelerator as a core component is dissolved or finely dispersed in a polyvalent isocyanate as a raw material of a wall film (shell) to form an oil phase. Next, the oil phase is dispersed in the form of oil droplets in an aqueous medium (aqueous phase) containing a dispersion stabilizer to prepare an O / W type (oil phase / aqueous phase type) emulsion. Next, a polyvalent amine is added to and dissolved in the aqueous phase of the O / W emulsion,
Interfacial polymerization with the polyvalent isocyanate in the oil phase causes a polyaddition reaction. Alternatively, by heating the O / W emulsion, the polyvalent isocyanate in the oil phase reacts with water at the interface with the aqueous phase to generate an amine, and subsequently causes a self-polyaddition reaction. In this way, the polyurea-based polymer, preferably the polyurea having the structural unit represented by the general formula (1) is converted into a shell portion (wall film).
The microcapsule dispersion liquid is obtained by preparing the microcapsules described below.

On the other hand, when a solid curing accelerator is dissolved in an organic solvent to form a core component, an S / O / W (solid phase / oil phase / water phase) type emulsion 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.

The organic solvent in this case is not particularly limited as long as it is liquid at room temperature, but it is necessary to select a solvent which does not dissolve at least the shell portion (wall film).
Specifically, in addition to organic solvents such as ethyl acetate, methyl ethyl ketone, acetone, methylene chloride, xylene, toluene, and tetrahydrofuran, phenylxylylethane,
Oils such as dialkylnaphthalene can be used.

[Second Step] A blocking agent is added to the microcapsule dispersion liquid obtained in the first step to dissolve or disperse. At this time, it is effective to add the blocking agent after once removing the dispersion stabilizer and unreacted amine in the aqueous phase by centrifugation or the like.

[Third Step] The microcapsule dispersion obtained by blocking the amino group with a blocking agent in the second step is
After removing the excess blocking agent by centrifugation or filtration, the powder is dried to produce a powdery microcapsule-type curing accelerator.

First, in the first step, the dispersion stabilizer to be added to the aqueous medium (aqueous phase) includes water-soluble polymers such as polyvinyl alcohol and hydroxymethyl cellulose, anionic surfactants, and nonionic surfactants. Agent,
Examples include surfactants such as cationic surfactants. In addition, hydrophilic inorganic colloids such as colloidal silica and viscous minerals can also be used. The addition amount of these dispersion stabilizers is preferably set so as to be 0.1 to 10% by weight in the aqueous phase.

The blocking agent used in the second step is not particularly limited as long as it is a compound having reactivity with an amino group. Examples thereof include an epoxy compound, an aldehyde compound, an acid anhydride and an ester. Compounds which react with amino groups such as compounds and isocyanate compounds to form a covalent bond are exemplified. Further, organic carboxylic acids such as acetic acid, formic acid, lactic acid, oxalic acid, and succinic acid, organic sulfonic acids such as p-toluenesulfonic acid, 2-naphthalenesulfonic acid, dodecylbenzenesulfonic acid, phenol compounds, boric acid, phosphoric acid, and nitric acid And acidic compounds which form a salt by neutralizing with amino groups such as inorganic acids such as nitrous acid and hydrochloric acid, and solid substances having an acidic surface such as silica and aerosil. Among these compounds, the above-mentioned acidic compounds are preferably used as compounds that effectively block amino groups present on the wall surface and inside the wall film, and formic acid and organic sulfonic acids are particularly preferably used.

The amount of the blocking agent to be added is such that the molar amount of the blocking agent is equivalent to that of the amino group present on the surface of the wall film and inside the wall film. Practically, for example, when an acidic compound is used as a blocking agent, an acidic substance (acidic compound) is added to the dispersion immediately after preparation of microcapsules (interfacial polymerization).
To adjust the pH of the dispersion from basic to acidic, preferably pH 2 to 5, and then remove excess acidic compounds by means such as centrifugation or filtration.

In the method for producing a microcapsule-type curing accelerator comprising the above first to third steps, as the second step, the unreacted free amine is obtained by passing the microcapsule dispersion through an acidic cation exchange resin column. Or a method of neutralizing residual amino groups.

The average particle size of the obtained microcapsule type curing accelerator is not particularly limited.
From the viewpoint of uniform dispersibility, the thickness is preferably set in the range of 0.05 to 500 μm, more preferably 0.1 to 3 μm.
0 μm. The shape of the microcapsule-type curing accelerator 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.

Further, in the microcapsule type curing accelerator, the amount of the curing accelerator included is preferably set to 10 to 95% by weight, particularly preferably 30 to 80% by weight, based on the total amount of the microcapsules. . That is, when the encapsulation amount of the curing accelerator is less than 10% by weight, the curing reaction time becomes too long and the reactivity becomes poor. Conversely, when the encapsulation amount of the curing accelerator exceeds 95% by weight, the thickness of the wall film increases. This is because there is a possibility that the core portion (curing agent) may be poor in isolation and mechanical strength.

The ratio of the thickness of the shell portion (wall film) to the particle size of the microcapsule type curing accelerator is 3 to 2
It is preferably set to 5%, particularly preferably 5 to 2%.
Set to 5%. 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 during the production of the epoxy resin composition,
On the other hand, if it exceeds 25%, the release of the included curing accelerator tends to be insufficient.

Then, the latent curing accelerator (C component)
Of the solid phenolic resin (component B) 100
It is preferable to set the amount to 0.1 to 40 parts by weight (hereinafter abbreviated as "part"). Particularly preferred is 5 to 20 parts. That is, the compounding amount of the latent curing accelerator,
If the amount is less than 0.1 part, the curing speed is too slow to cause a decrease in the strength, and if it exceeds 40 parts, the curing speed is too fast and the fluidity may be impaired.

In the present invention, a commercially available microcapsule-type curing accelerator is used as the latent curing accelerator, which is the component C, unless the intended purpose is impaired, in addition to the above-mentioned microcapsules containing the curing accelerator. be able to.
Examples of commercially available products include MCE-9957 (trade name, manufactured by Nippon Kayaku Co., Ltd., which uses methyl methacrylate as a wall film), and NOVACURE (trade name, HX) manufactured by Asahi Ciba.
-3748, 3741, 3742, HX-3921H
R, HX-3941HP) and the like. Further, even if a curing accelerator other than the microcapsule-type curing accelerator, dicyandiamide, or those having weak catalytic activity such as Fuji Cure FXR-1030 and FXE-1000 manufactured by Fuji Kasei Kogyo Co., Ltd., or a normal curing accelerator The catalyst activity may be weakened by adding a small amount.

The inorganic filler (component D) used together with the components A to C is not particularly limited, and various inorganic fillers can be used. For example, silica, clay, gypsum, calcium carbonate, barium sulfate,
Alumina oxide, beryllium oxide, silicon carbide, silicon nitride, aerosil and the like, nickel, gold, copper,
Conductive particles such as silver, tin, lead, and Bi may be added. Among them, spherical silica powder, specifically, spherical fused silica powder is particularly preferably used. Furthermore, the average particle size is 0.0
It is preferably in the range of 1 to 60 µm, more preferably in the range of 0.1 to 15 µm. In the present invention, the term “spherical” refers to a flow type particle image analyzer (SYSM).
EX refers to an average sphericity of 0.85 or more measured using FPIA-100 manufactured by EX Corporation.

The content ratio of the inorganic filler (D component) is 15 to 85 in the whole resin composition for semiconductor encapsulation.
It is preferably set so as to be 50% by weight, particularly preferably 50 to 80% by weight. That is, when the content ratio of the inorganic filler is less than 15% by weight, the viscosity at 25 ° C. becomes low, and the inorganic filler tends to settle during storage, or the moisture absorption rate becomes high, and the moisture resistance reliability tends to deteriorate. And
If it exceeds 85% by weight, the fluidity tends to decrease, and the discharge and coating workability tends to deteriorate.

Further, in addition to the above-mentioned components A to D, other additives can be appropriately blended with the resin composition for semiconductor encapsulation of the present invention, if necessary.

Examples of the other additives include a flame retardant,
Wax, leveling agent, defoamer, flux, pigment,
Dyes, silane coupling agents, titanate coupling agents and the like can be mentioned. Examples of the silane coupling agent include γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexylethyltrimethoxysilane), γ-methacryloxypropyltrimethoxysilane. Examples thereof include methoxysilane and amino group-containing silane, and these may be used alone or in combination of two or more.

Examples of the flame retardant include metal compounds such as novolak type brominated epoxy resin, brominated bisphenol A type epoxy resin, antimony trioxide, antimony pentoxide, magnesium hydroxide and aluminum hydroxide, red phosphorus, phosphorus Examples thereof include phosphorus compounds such as acid esters, which are used alone or in combination of two or more.

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

Further, in addition to the above-mentioned other additives, components such as silicone oil, silicone rubber, synthetic rubber, and a reactive diluent are added to the resin composition for semiconductor encapsulation of the present invention to reduce stress. An ion trapping agent such as hydrotalcites and bismuth hydroxide may be blended for the purpose of improving the reliability in the humidity resistance reliability test.

The resin composition for encapsulating a semiconductor of the present invention can be produced, for example, as follows. That is, after mixing the above-mentioned components A to D and other additives as necessary, the mixture is kneaded in a kneading machine such as a universal stirrer in a heated state and melt-mixed. Next, by cooling this at room temperature (about 25 ° C.), the intended resin composition for encapsulating a semiconductor can be produced. In addition, an organic solvent may be added to adjust the fluidity of the resin composition for semiconductor encapsulation. Examples of the organic solvent include toluene, xylene, methyl ethyl ketone (MEK), acetone, diacetone alcohol and the like. These may be used alone or in combination of two or more.

The viscosity of the resin composition for semiconductor encapsulation thus obtained must be set to not less than 7,000 poise at 25 ° C. and not more than 5000 poise at 80 ° C. Particularly preferably, at 25 ° C., 700
0 poise or more and 3000 poise at 80 ° C
It is as follows. That is, when the temperature is less than 7000 poise at 25 ° C. and more than 5000 poise at 80 ° C., storage stability, discharge and coating workability are deteriorated, and initial characteristics cannot be satisfied.

The above-mentioned resin composition for semiconductor encapsulation 25
Each viscosity at ° C and 80 ° C is measured at each of the above temperatures using an E-type viscometer. Specifically, it is as shown below.

[Viscosity at 25 ° C.] RE manufactured by Toki Sangyo Co., Ltd.
In the 80U type, the rotor uses 3 ° × R7.7, and after pretreatment for 1 minute at a cone rotor rotation speed of 1 rpm, 1 rpm at 0.1 rpm.
The value after standing for 0 minutes is measured.

[Viscosity at 80 ° C.] RE manufactured by Toki Sangyo Co., Ltd.
For the 80R type, a rotor having a viscosity of less than 1000 poise uses a rotor 3 ° × R14, and a rotor having a viscosity of 1000 poise or more uses a rotor 3 ° × R7.7, and after pretreatment for 1 minute at a cone rotor rotation speed of 1 rpm, at 0.5 rpm. The value after standing for 10 minutes is measured.

The production of a semiconductor device using the resin composition for encapsulating a semiconductor of the present invention can be performed by various conventionally known methods. For example, in mounting by flip chip, COB, graph top, cavity fill, etc., the above-mentioned resin composition for semiconductor encapsulation heated (about 40 to 90 ° C., preferably about 60 to 80 ° C.) is dispensed with a dispenser. After being used and potting, the semiconductor device can be manufactured by heating and curing to form a sealing resin layer. Further, without heating in advance, a solid or semi-solid semiconductor encapsulating resin composition is directly attached or coated on a semiconductor element or the like, and then heated and cured to form an encapsulating resin layer. Thus, a semiconductor device can be manufactured. Note that the above mounting may be performed under vacuum.

The flip chip mounting of the above-described semiconductor device manufacturing method will be specifically described by way of a side fill sealing method, a press bump sealing method, and a print sealing method as examples.

[Side-Fill Sealing Method] First, a device in which a semiconductor element is mounted on a printed circuit board via a plurality of connection electrodes is prepared. Then, pre-heating (40-13
The above semiconductor encapsulation heated (about 40 to 90 ° C., preferably about 60 to 80 ° C.) in the gap between the printed circuit board and the semiconductor element which has been heated to about 0 ° C., preferably about 60 to 100 ° C.) A semiconductor device by flip-chip mounting can be manufactured by injecting and filling a resin composition for use with a dispenser, heating and curing to form a sealing resin layer.

The solid or semi-solid resin composition for semiconductor encapsulation is directly adhered to or applied to the semiconductor element or in the vicinity thereof without heating beforehand, and then heated and cured to cure the semiconductor. It is also possible to form a sealing resin layer in the gap between the element and the printed circuit board.

The production of a semiconductor device by the above-described side-fill sealing method may be performed under vacuum. As an apparatus to be performed under vacuum, there is, for example, a model MBC-V series manufactured by Musashi Engineering Co., Ltd. or the like. Further, when manufacturing the semiconductor device under the vacuum, after filling and filling the gap between the printed circuit board and the semiconductor element under vacuum using a dispenser with a resin composition for semiconductor encapsulation, and then returned to atmospheric pressure Differential pressure filling of filling a resin composition for semiconductor encapsulation may be performed.

[Press Bump Sealing Method] First, the printed circuit board is heated (about 40 to 90 ° C., preferably 60 to 80 ° C.).
The above-mentioned resin composition for semiconductor encapsulation which has been subjected to potting is potted using a dispenser. Thereafter, a semiconductor device by flip-chip mounting can be manufactured by forming a sealing resin layer at the same time as electrical connection between the semiconductor element and the printed circuit board by a press bump connection method using a flip chip bonder or the like.

A solid or semi-solid resin composition for semiconductor encapsulation is directly adhered or applied to a semiconductor element or a wiring circuit board without heating in advance, and then the semiconductor is applied by a press bump connection method. It is also possible to form the sealing resin layer simultaneously with the electrical connection between the element and the printed circuit board.

The manufacture of a semiconductor device by the above-described press bump sealing method may be performed under vacuum if necessary.

Instead of potting using a dispenser, if possible, coating is performed by printing, and then, simultaneously with electrical connection between the semiconductor element and the wiring circuit board by a press bump connection method using a flip chip bonder or the like. A sealing resin layer may be formed. The application by printing may be performed by heating the entire printing atmosphere or partially heating a mask, a squeegee, or the like (a heating target is 40 to
100 ° C).

[Print Sealing Method] First, a printed circuit board on which a semiconductor element is mounted via a plurality of connection electrodes is prepared. Then, heating (approximately 40 to 90 ° C., preferably 60 to 80 ° C.) is performed in the gap between the printed circuit board and the semiconductor element which has been preliminarily heated (approximately 40 to 130 ° C., preferably approximately 60 to 100 ° C.) The above-described resin composition for semiconductor encapsulation is dropped using a dispenser, and a sealing resin layer is formed by print encapsulation, whereby a semiconductor device by flip-chip mounting can be manufactured.

As for the above-mentioned printing sealing, a vacuum printing sealing device (model VPE-100 series) manufactured by Toray Engineering Co., Ltd. using a vacuum differential pressure is used because air bubbles hardly enter the sealing resin layer. preferable.

It is also possible to apply a solid or semi-solid resin composition for semiconductor encapsulation directly to a stage, a squeegee or the like without heating them in advance, to perform coating, etc., and to perform print encapsulation. .

On the other hand, a method of manufacturing a cavity-filled semiconductor device among the above-described methods of manufacturing a semiconductor device will be specifically described.

First, a semiconductor element mounted on a printed circuit board and electrically connected to each other by a bonding wire or the like is prepared. Then, preheating (40 to 130)
The above resin composition for semiconductor encapsulation, which is heated (about 40 to 90 ° C., preferably about 60 to 80 ° C.) to the printed circuit board and the semiconductor element which have been heated to about 40 ° C., preferably about 60 to 100 ° C. Is potted using a dispenser, and heat-cured to form a sealing resin layer so as to incorporate a semiconductor element, whereby a cavity-filled semiconductor device can be manufactured.

A solid or semi-solid semiconductor encapsulating resin composition is directly adhered or applied without prior heating, and then heated and cured to encapsulate the semiconductor element. It is also possible to form a resin layer.

The manufacture of the semiconductor device by the above sealing method may be performed under vacuum. As an apparatus to be performed under vacuum, for example, model MBC-V manufactured by Musashi Engineering Co., Ltd.
Series.

Next, another manufacturing method will be described. That is,
First, a device in which a semiconductor element is mounted on a printed circuit board and both are electrically connected by a bonding wire or the like is prepared. Then, heating (approximately 40 to 90 ° C., preferably 60 to 8 ° C.) is performed on the printed circuit board and the semiconductor element which have been heated (approximately 40 to 130 ° C., preferably approximately 60 to 100 ° C.) in advance.
The above-mentioned resin composition for semiconductor encapsulation (about 0 ° C.) is supplied by printing or the like, and is heated and cured to form an encapsulation resin layer so as to incorporate a semiconductor element, thereby manufacturing a cavity-filled semiconductor device. can do.

The production of a semiconductor device by the above-described print sealing is as follows.
It may be performed under vacuum. Furthermore, when manufacturing a semiconductor device under vacuum, after printing and sealing under vacuum, the air pressure of the atmosphere is increased to remove voids in the semiconductor sealing resin composition,
Further finishing printing may be performed in that state.

The semiconductor device thus obtained is used, for example, for mounting a mounting substrate (motherboard) and is used for manufacturing a semiconductor product. That is, a semiconductor device is mounted on a mounting board (mother boat) with its own wiring circuit board facing through a plurality of connection electrode portions, and the mounting board and the semiconductor device are connected to each other. The gaps between them are filled with the resin composition for semiconductor encapsulation of the present invention, and are cured by heating to form an encapsulation resin layer, thereby producing a semiconductor product.

The method of heating and curing the resin composition for semiconductor encapsulation is not particularly limited, and examples thereof include a convection dryer, an IR reflow oven, and a heating method using a hot plate. .

The method for filling the gap between the mounting substrate and the semiconductor device by using the resin composition for semiconductor encapsulation of the present invention includes, for example, the flip-flop method of the above-described method for manufacturing a semiconductor device. The same method as described for the chip mounting, a side-fill sealing method, a press bump sealing method, a printing sealing method, and the like can be used. A conductive paste such as nickel, gold, silver, or copper is dispersed in the above resin composition for semiconductor encapsulation to form an ACF (Anisotropic Conductor).
ve Film), ACP (Anisotropic Conductive Paste)
May be used for flip chip mounting. As another usage method, the above resin composition for semiconductor encapsulation may be used as a dam material on a printed circuit board, or as a die bonding agent or an adhesive between a heat sink and a printed circuit board.

Next, examples will be described together with comparative examples.

First, prior to the examples, the following components were prepared.

[Epoxy resin a1] Bisphenol F type epoxy resin (liquid at 25 ° C .: epoxy equivalent: 158 g /
ep, Epototo YDF-8170 manufactured by Toto Kasei).

[Epoxy resin a2] bisphenol A type epoxy resin (liquid at 25 ° C: epoxy equivalent 170 g /
Ep, DER-332 manufactured by Dow Chemical Company).

[Epoxy resin a3] Alicyclic epoxy resin (liquid at 25 ° C: epoxy equivalent 135 g / ep, Celloxide 2021P manufactured by Daicel Chemical Industries, Ltd.).

[Phenol resin b1] A tetrafunctional solid phenol resin represented by the following chemical formula (a) (solid at 25 ° C .: melting point: 187 ° C., purity: 94%, THD-2344 manufactured by Honshu Chemical Industry Co., Ltd.).

[0096]

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[Phenol resin b2] A pentafunctional solid phenol resin represented by the following chemical formula (b) (solid at 25 ° C: melting point: 182 ° C, purity: 97.5%, BisPG-26X manufactured by Honshu Chemical Industry Co., Ltd.).

[0098]

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[Phenol resin b3] A tetrafunctional solid phenol resin represented by the following chemical formula (C) (solid at 25 ° C .: melting point: 156 ° C., purity: 93.6%, MHD-2344 manufactured by Honshu Chemical Industry Co., Ltd.).

[0100]

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[Phenol resin b4] A trifunctional solid phenol resin represented by the following chemical formula (d) (solid at 25 ° C .: melting point: 94 ° C., purity: 98%, H: Honshu Chemical Industry Co., Ltd.)
DM-234).

[0102]

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[Phenol resin b5] A solid phenol resin represented by the following chemical formula (e) (solid at 25 ° C .:
Melting point 95 ° C, purity 89%, Tris manufactured by Honshu Chemical Industry Co., Ltd.
P-RK).

[0104]

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[Phenol resin b6] Triphenylmethane type phenol resin [solid at 25 ° C .: hydroxyl equivalent 101
g / ep, melting point 110 ° C, viscosity at 150 ° C 3-4 pois
e, MEH-7500 (3,4P) manufactured by Meiwa Kasei Co., Ltd.].

[Phenol resin b7] A p-ethylphenol resin represented by the following chemical formula (f) (solid at 25 ° C: hydroxyl equivalent: 129 g / ep, melting point: 98 ° C, manufactured by Meiwa Kasei Co., Ltd.).

[0107]

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[Phenol resin b8] Allylated phenol novolak (liquid at 25 ° C .: hydroxyl equivalent 135 g / e
p, MEH-8005H manufactured by Showa Kasei Co., Ltd.).

[Acid anhydride-based curing agent] Methyl hexahydrophthalic anhydride (methylated HHPA, RIKACID MH-700 manufactured by Shin Nippon Rika Co., Ltd.).

[Curing Accelerator c1] A microcapsule-type curing accelerator was prepared according to the method described above. That is,
First, 11 parts of an adduct of 3 mol of xylylene diisocyanate and 1 mol of trimethylolpropane and 4.6 parts of an adduct of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane were added to triphenylphosphine 7 as a curing accelerator. And 3.9 parts of ethyl acetate were uniformly dissolved in a mixture to prepare an oil phase. Separately, an aqueous phase composed of 100 parts of distilled water and 5 parts of polyvinyl alcohol was separately prepared,
The oil phase prepared above was added thereto, and the mixture was emulsified with a homomixer 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, 10 parts of an aqueous solution containing 3 parts of triethylenetetramine was prepared, placed in the dropping funnel provided in the polymerization reactor, dropped into the emulsion in the reactor, and subjected to interfacial polymerization at 70 ° C. for 3 hours. Was carried out to obtain an aqueous suspension of a microcapsule-type curing accelerator. Subsequently, after removing polyvinyl alcohol and the like in the aqueous phase by centrifugation, 100 parts of distilled water was added and dispersed again to obtain a suspension.

Formic acid was added dropwise to this suspension to adjust the pH of the system to 3. Thus, a microcapsule-type curing accelerator in which amino groups on the wall surface and inside were blocked by formic acid was prepared. The microcapsule-type curing accelerator thus obtained was separated as centrifugal separation, washed repeatedly with water, and dried to isolate as free-flowing powdery particles. The average particle size of the microcapsule-type curing accelerator was 2 μm. The shell thickness ratio to the microcapsule particle size is 15%.
And the encapsulation amount of triphenylphosphine is 30
% By weight.

[Curing accelerator c2] MCE manufactured by Nippon Kayaku Co., Ltd.
-9957.

[Curing accelerator c3] 2-Ethyl-4-methylimidazole (Curesol 2E manufactured by Shikoku Chemicals Co., Ltd.)
4MZ).

[Inorganic filler d1] Spherical fused silica powder (average particle size 5.0 μm, SP-4B manufactured by Tonen Chemical Co., Ltd.).

[Inorganic filler d2] Spherical fused silica powder (average particle size: 15 μm, FB-48 manufactured by Denki Kagaku Kogyo KK)
X).

[Inorganic filler d3] Spherical fused silica powder (average particle size: 0.56 μm, SE-Made by Admatechs, Inc.)
2100)

[0118]

Examples 1 to 12, Comparative Examples 1 to 4, and Conventional Examples The above components were blended in the proportions shown in Tables 1 to 3 below, and kneaded and melt-mixed in a universal stirring kettle. Next, this was cooled at room temperature to produce a desired resin composition for semiconductor encapsulation. The kneading conditions are as shown below.

[Examples 1 to 8, Comparative Example 4] First, an epoxy resin and a phenol resin were charged and mixed at 150 ° C for 2 minutes to dissolve all solids. Next, 90-100 ° C
The temperature was lowered until the mineral filler was added and mixed for 10 minutes. Then, after the temperature was adjusted to 75 ° C., a curing accelerator was added, mixed for 2 minutes, and received.

[Examples 9 to 12, Comparative Examples 2 and 3]
Epoxy resin and phenol resin are charged.
Mix for minutes to dissolve all solids. Next, 90-1
The temperature was lowered to 00 ° C, the inorganic filler was added and mixed for 10 minutes. After the temperature was adjusted to 65 ° C., a curing accelerator was added and mixed for 2 minutes and received.

[Comparative Example 1, Conventional Example] First, an epoxy resin, a phenol resin or an acid anhydride was charged and mixed at 80 ° C. for 10 minutes. Thereafter, the inorganic filler was added at the same temperature and mixed for 10 minutes. Then, the temperature was lowered to 50 ° C., a curing accelerator was added, and the mixture was mixed for 2 minutes and received.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

The thus obtained resin compositions for semiconductor encapsulation of Examples and Comparative Examples were prepared at 25 ° C. and 8 ° C.
Each viscosity at 0 ° C. was measured using an E-type viscometer according to the method described above. Further, the glass transition temperature (Tg), the storage stability (the degree of sedimentation of the inorganic filler, the degree of change in viscosity), the discharge and coating workability, and the pot life were measured and evaluated according to the following methods. Further, the moisture resistance reliability of a semiconductor device manufactured using the above resin composition for semiconductor encapsulation was measured and evaluated according to the following method. The results are shown in Tables 4 to 7 below.

[Glass Transition Temperature (Tg)] A test piece obtained by curing a defoaming-treated resin composition for semiconductor encapsulation at 150 ° C. for 3 hours was applied to a TMA device (Model No. M, manufactured by Rigaku Corporation).
G800GM). The measurement was performed at a temperature rise of 5 ° C./min with a load of 30 g. Then, a graph is created in which the horizontal axis represents temperature and the vertical axis represents elongation.
The intersection of the tangent between 200 ° C and 200 ° C to 230 ° C is Tg
Asked.

[Storage Stability] * 1: Degree of sedimentation of inorganic filler The resin composition for semiconductor encapsulation is placed in a test tube having an inner diameter of 16 mm and a height of 180 mm, and sealed (sample height: 120 m).
m) After standing at 25 ° C. for 30 days, the degree of sedimentation of the inorganic filler was confirmed. When the inorganic filler settled, the turbidity level of the resin composition for semiconductor encapsulation was changed when the inorganic filler was settled.
Those with reduced turbidity (increased transparency) were considered to have sedimentation. When the height of the sedimentation portion was 1 mm or more, x was indicated as having sedimentation, and when there was no sedimentation portion, ◎ was indicated as no sedimentation. * 2: Degree of change in viscosity The sample was left to stand in an atmosphere at 25 ° C (30 days), and the viscosity before and after standing was measured using an E-type viscometer (measuring temperature: 80 ° C, measuring temperature: 25 ° C for the conventional example). . When the viscosity after standing is 1.5 times or less of the viscosity before standing, ◎ is given, and when the viscosity after leaving is more than 1.5 times the viscosity before leaving 3.0 times or less, ○ is given. Was marked with a symbol of “△” when the viscosity was more than 3.0 times and less than or equal to 10 times the viscosity before being left, and was marked with “x” when the viscosity after standing was more than 10 times of the viscosity before being left. The measurement of the viscosity using an E-type viscometer was performed in the same manner as the method of measuring the viscosity at 25 ° C. or 80 ° C.

[Dischargeability and Coating Workability] The discharge amount when the semiconductor sealing resin composition heated to 80 ° C. was discharged using a dispenser under constant conditions of time and pressure was evaluated. That is, a syringe 10c manufactured by Musashi Engineering Co., Ltd.
c, Using a metal needle SN-17G (inner diameter 2.4 mm), the discharge amount after 10 seconds at a pressure of 5 kg / cm ² was measured. As a result, those with a discharge amount of 1000 mg or more
の も の, 50 mg for 200 mg or more and less than 1000 mg
Those with less than 200 mg were rated as Δ, and those with less than 50 mg were rated as x. If the amount is less than 50 mg under the above conditions, the resin sealing of the semiconductor is at an impossible level.

[Working time (change in viscosity)] The viscosity of each resin composition for semiconductor encapsulation before and after standing at 50 ° C for 72 hours was measured using an E-type viscometer (measuring temperature: 80 ° C, conventional example). (Measuring temperature: 25 ° C.). When the viscosity after standing is 1.5 times or less of the viscosity before standing, ◎ is given, and when the viscosity after leaving is more than 1.5 times the viscosity before leaving 3.0 times or less, ○ is given. Was marked with a symbol of “△” when the viscosity was more than 3.0 times and less than or equal to 10 times the viscosity before being left, and was marked with “x” when the viscosity after standing was more than 10 times of the viscosity before being left. The measurement of the viscosity using an E-type viscometer was performed in the same manner as the method of measuring the viscosity at 25 ° C. or 80 ° C.

[Humidity Reliability] A semiconductor device was manufactured as follows using each of the above-mentioned resin compositions for encapsulating a semiconductor. That is, first, a dual in-line package (DIP) frame on which a semiconductor chip is mounted is set in a DIP mold, and the mold is heated to 140 ° C. (1 in the conventional example).
10 ° C). Then, a defoaming process is performed in advance, and 60 to 12
A molten resin composition for encapsulating a semiconductor heated to 0 ° C. was added dropwise, and cured at 150 ° C. for 3 hours (the conventional example was cured at 110 ° C. for 20 hours) to produce a semiconductor device. . Then, at 130 ° C. × 85% RH × 2.
3atm (applied bias: 30V) is applied, and the conduction of each pattern is checked. In addition, the continuity check was performed after taking out to room temperature. The time when the defect rate of the package [(the number of defective patterns / the total number of patterns) × 100] became 50% or more was confirmed. The other conditions are as follows.・ Evaluation package: DIP16 ・ Lead frame: 4.2 alloy, thickness 0.25 mm ・ Chip: Full-size Al model element 3 × 6 mm made by Shinko (Al pattern thickness 5 μm, width 5 μm) ・ Wire: 99.99% Gold SR Ag paste: EN-4000 manufactured by Hitachi Chemical Co., Ltd. Evaluation number: 10 packages / sample (40 patterns can be measured in total because 2 patterns of + poles and 2 patterns of-poles are wired in one package) PCT condition: 130 ° C x 85% RH x 2.3 atm (applied bias 30V)

[0131]

[Table 4]

[0132]

[Table 5]

[0133]

[Table 6]

[0134]

[Table 7]

From the results of Tables 4 to 7, it can be seen that all the products of Examples have no sedimentation of the inorganic filler, have a longer pot life and are excellent in storage stability as compared with the conventional products. Understand. Further, it can be seen that the ejection and coating workability is excellent, and that the obtained semiconductor device has good moisture resistance reliability. In particular, the products of Examples 1 to 9 use a polyfunctional solid phenol resin as the solid phenol resin, and therefore have a higher glass transition temperature than those using a solid phenol resin that is not a polyfunctional solid phenol resin. I have. Further, the products of Examples 1 and 3 to 12 use a specific microcapsule-type hardening accelerator as a latent hardening accelerator. The service life is very long and the storage stability is particularly excellent.

On the other hand, since the product of Comparative Example 1 uses the liquid epoxy resin and the liquid phenol resin, the storage stability is deteriorated, and it can be seen that the inorganic filler is settled. The product of Comparative Example 2 also has a viscosity of 7000 at 25 ° C.
Since it is less than poise, it can be seen that sedimentation of the inorganic filler has occurred. Furthermore, since the product of Comparative Example 3 uses a curing accelerator that is not a latent curing accelerator, it can be seen that the pot life is short and the viscosity change during storage is large. And, since the viscosity of the resin composition for semiconductor encapsulation exceeds 5,000 poise at 80 ° C. in the product of Comparative Example 4, it can be seen that the discharge and coating workability is deteriorated.

Next, an embodiment relating to a method of manufacturing the semiconductor device will be described.

[0138]

Example 13 A semiconductor device was manufactured as follows using a resin composition for semiconductor encapsulation prepared in Example 4 which had been defoamed under reduced pressure at 70 ° C. in advance. That is, 70 ° C. is placed on a printed circuit board preheated to 100 ° C.
The heated semiconductor encapsulating resin composition was potted using a dispenser. Then, using a flip chip bonder, the semiconductor element is mounted on the printed circuit board, and connected by thermocompression bonding (conditions: 150 ° C. × 2 kg × 30 minutes + 2
(20 ° C. × 0.5 kg × 2 minutes) to electrically connect the semiconductor element and the wiring circuit board by the connection electrode portion, and at the same time, to form a sealing resin layer in the gap between the wiring circuit board and the semiconductor element, thereby flipping Semiconductor devices were manufactured by chip mounting.

[0139]

Example 14 The resin composition for semiconductor encapsulation prepared in Example 5 was subjected to defoaming under reduced pressure at 70 ° C. in advance. Otherwise, the procedure of Example 13 was followed to fabricate a semiconductor device by flip-chip mounting.

[0140]

Example 15 A semiconductor device was manufactured in the following manner by using the resin composition for semiconductor encapsulation prepared in Example 9 which had been defoamed under reduced pressure at 70 ° C. in advance. That is, a device in which a semiconductor element was mounted on a printed circuit board and both were electrically connected by a bonding wire was prepared. Then, the above-mentioned resin composition for semiconductor encapsulation, which was heated to 70 ° C., was applied by printing through an opening of a mask under a vacuum of 5 Torr on the printed circuit board and the semiconductor element which were previously heated to 70 ° C. Next, the atmospheric pressure is set to 150 To
rr, the voids in the resin composition for semiconductor encapsulation are removed, and final printing is performed using the resin composition for semiconductor encapsulation heated to 70 ° C. while maintaining the state of 150 Torr. went. Thereafter, the semiconductor device was cured by heating under a condition of 150 ° C. × 3 hours to form a sealing resin layer so as to incorporate the semiconductor element, thereby manufacturing a cavity-filled semiconductor device.

[0141]

Example 16 The resin composition for semiconductor encapsulation prepared in Example 10 was defoamed under reduced pressure at 70 ° C. in advance. Otherwise, the procedure of Example 13 was followed to fabricate a semiconductor device by flip-chip mounting.

[Preparation of Resin Composition α for Semiconductor Encapsulation] The above components were mixed in the mixing ratio shown in Table 8 below, kneaded and melt-mixed in a universal stirring vessel, and then vacuum-evacuated at 70 ° C. I foamed. Next, this was cooled at room temperature to produce a desired resin composition for semiconductor encapsulation. The kneading conditions are as shown below. That is,
First, charge epoxy resin and phenol resin,
C. for 2 minutes to dissolve all solids. Next, 9
Lower the temperature to 0-100 ° C, add inorganic filler and add 1
Mix for 0 minutes. And after adjusting to a temperature of 75 ° C,
The curing accelerator was added and mixed for 2 minutes and accepted.

With respect to the obtained resin composition α for semiconductor encapsulation, the respective viscosities at 25 ° C. and 80 ° C. were measured using an E-type viscometer according to the method described above. Further, the glass transition temperature (Tg), storage stability (the degree of sedimentation of the inorganic filler, the degree of change in viscosity), the discharge and coating workability, and the pot life were measured and evaluated in the same manner as described above. Further, the moisture resistance reliability of the semiconductor device manufactured using the resin composition for semiconductor encapsulation α was measured and evaluated according to the same method as described above. The results are shown in Table 8 below.
Are also shown.

[0144]

[Table 8]

[0145]

Example 17 Using the above resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board via a connection electrode portion was prepared. The gap between the printed circuit board and the semiconductor element preheated to 100 ° C.
Was filled with the heated semiconductor sealing resin composition α using a dispenser. Thereafter, the semiconductor device was flip-chip mounted by heating and curing at 150 ° C. × 3 hours to form a sealing resin layer in the gap between the printed circuit board and the semiconductor element.

[0146]

Example 18 Using the resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board via a connection electrode portion was prepared. Then, 5 Torr is applied to the gap between the printed circuit board and the semiconductor element which has been heated to 70 ° C. in advance.
The semiconductor sealing resin composition α heated to 70 ° C. under a vacuum of r was filled using a dispenser. Then 15
A semiconductor device by flip-chip mounting was manufactured by heating and curing at 0 ° C. × 3 hours to form a sealing resin layer in a gap between the printed circuit board and the semiconductor element.

[0147]

Example 19 Using the semiconductor encapsulating resin composition α,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board via a connection electrode portion was prepared. Then, 5 Torr is applied to the gap between the printed circuit board and the semiconductor element which has been heated to 70 ° C. in advance.
The semiconductor sealing resin composition α heated to 70 ° C. under a vacuum of r was filled using a dispenser. Thereafter, the pressure is further returned to the atmospheric pressure, and the semiconductor encapsulating resin composition α heated to 70 ° C. is filled (differential pressure filling).
A semiconductor device by flip-chip mounting was manufactured by heating and curing over time to form a sealing resin layer in a gap between the printed circuit board and the semiconductor element.

[0148]

Example 20 Using the above-mentioned resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, the semiconductor encapsulating resin composition α heated to 70 ° C. was potted on a printed circuit board previously heated to 100 ° C. using a dispenser. After that, using a flip chip bonder, a semiconductor element is mounted on the wiring circuit board,
Thermo-compression connection (conditions: 150 ° C x 2 kg x 30 minutes + 220
(° C. × 0.5 kg × 2 minutes) to electrically connect the semiconductor element and the printed circuit board by the connection electrode portion, and at the same time, form a sealing resin layer in a gap between the printed circuit board and the semiconductor element, thereby flip chip. A semiconductor device was manufactured by mounting.

[0149]

Example 21 Using the resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, the semiconductor encapsulating resin composition α heated to 70 ° C. was potted on a semiconductor element previously heated to 100 ° C. using a dispenser. Thereafter, using a flip chip bonder, a wiring circuit board heated to 70 ° C. is mounted on the semiconductor element, and connected by thermocompression bonding (conditions: 150 ° C. × 2 kg)
(× 30 minutes + 220 ° C. × 0.5 kg × 2 minutes) to electrically connect the semiconductor element and the printed circuit board with the connecting electrode portion, and at the same time, form a sealing resin layer in a gap between the printed circuit board and the semiconductor element. Thus, a semiconductor device by flip-chip mounting was manufactured.

[0150]

Example 22 Using the semiconductor encapsulating resin composition α,
A semiconductor device was manufactured as follows. That is, the semiconductor encapsulating resin composition α heated to 70 ° C. was potted on a pre-heated 70 ° C. printed circuit board under a vacuum of 5 Torr using a dispenser. afterwards,
A semiconductor element is mounted on the printed circuit board using a flip chip bonder, and connected by thermocompression bonding (condition: 150 ° C. × 2
(kg × 30 minutes + 220 ° C. × 0.5 kg × 2 minutes) to electrically connect the semiconductor element and the printed circuit board with the connecting electrode portion, and at the same time, form a sealing resin layer in a gap between the printed circuit board and the semiconductor element. As a result, a semiconductor device by flip-chip mounting was manufactured.

[0151]

Example 23 Using the semiconductor encapsulating resin composition α,
A semiconductor device was manufactured as follows. That is, the semiconductor encapsulating resin composition α heated to 70 ° C. was potted on a semiconductor element previously heated to 70 ° C. using a dispenser under a vacuum of 5 Torr. After that, using a flip chip bonder, 70
The printed circuit board heated to ℃ is mounted and connected by thermocompression bonding (conditions: 150 ℃ x 2 kg x 30 minutes + 220 ℃ x 0.5 kg)
X 2 minutes) to electrically connect the semiconductor element and the printed circuit board by the connection electrode portion, and at the same time, form a sealing resin layer in the gap between the printed circuit board and the semiconductor element, thereby realizing a flip-chip mounted semiconductor device. Manufactured.

[0152]

Example 24 Using the semiconductor encapsulating resin composition α,
A semiconductor device was manufactured as follows. That is, the semiconductor encapsulating resin composition α heated to 70 ° C. was applied by printing through the opening of the mask onto a semiconductor element heated to 70 ° C. in advance. Thereafter, using a flip chip bonder, a wiring circuit board heated to 70 ° C. is mounted on the semiconductor element, and connected by thermocompression bonding (conditions: 150 ° C. × 2 kg)
(× 30 minutes + 220 ° C. × 0.5 kg × 2 minutes) to electrically connect the semiconductor element and the printed circuit board with the connecting electrode portion, and at the same time, form a sealing resin layer in a gap between the printed circuit board and the semiconductor element. Thus, a semiconductor device by flip-chip mounting was manufactured.

[0153]

Example 25 Using the resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, the semiconductor encapsulating resin composition α heated to 70 ° C. was applied by printing through a mask opening to a printed circuit board heated to 70 ° C. in advance. After that, using a flip chip bonder, a semiconductor element is mounted on the wiring circuit board,
Thermo-compression connection (conditions: 150 ° C x 2 kg x 30 minutes + 220
(° C. × 0.5 kg × 2 minutes) to electrically connect the semiconductor element and the printed circuit board by the connection electrode portion, and at the same time, form a sealing resin layer in a gap between the printed circuit board and the semiconductor element, thereby flip chip. A semiconductor device was manufactured by mounting.

[0154]

Example 26 Using the above-mentioned semiconductor sealing resin composition α,
A semiconductor device was manufactured as follows. That is, the semiconductor encapsulating resin composition α heated to 70 ° C. was applied by printing through a mask opening under a vacuum of 5 Torr on a semiconductor element previously heated to 70 ° C. afterwards,
Using a flip chip bonder, 7
A printed circuit board heated to 0 ° C. is mounted and connected by thermocompression bonding (conditions: 150 ° C. × 2 kg × 30 minutes + 220 ° C. × 0.5
(kg × 2 minutes), the semiconductor device and the printed circuit board are electrically connected by the connection electrode portion, and at the same time, the sealing resin layer is formed in the gap between the printed circuit board and the semiconductor element, thereby enabling the semiconductor device to be flip-chip mounted. Was manufactured.

[0155]

Example 27 Using the semiconductor encapsulating resin composition α,
A semiconductor device was manufactured as follows. That is, the resin composition for semiconductor encapsulation α heated to 70 ° C. was applied by printing through an opening of a mask under a vacuum of 5 Torr onto a printed circuit board previously heated to 70 ° C. Then, using a flip chip bonder, the semiconductor element is mounted on the printed circuit board and connected by thermocompression bonding (condition: 150 ° C.).
(× 2 kg × 30 minutes + 220 ° C. × 0.5 kg × 2 minutes) to electrically connect the semiconductor element and the wiring circuit board by the connection electrode portion, and at the same time, to form a sealing resin layer in the gap between the wiring circuit board and the semiconductor element. By the formation, a semiconductor device by flip-chip mounting was manufactured.

[0156]

Example 28 Using the above resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board and both were electrically connected by a bonding wire was prepared. Then, on a semiconductor element which has been heated to 100 ° C. in advance, 70
The semiconductor encapsulating resin composition α heated to ° C. was potted using a dispenser. After that, 150 ℃ × 3
A cavity-fill type semiconductor device was manufactured by forming a sealing resin layer so as to incorporate a semiconductor element by heating and curing in a time.

[0157]

Example 29 Using the above-mentioned resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board and both were electrically connected by a bonding wire was prepared. Then, the semiconductor device is heated to 70 ° C.
Semiconductor encapsulation resin composition α heated to 5 Torr
Potted using a dispenser under vacuum.
Thereafter, the semiconductor device was cured by heating at 150 ° C. for 3 hours to form a sealing resin layer so as to incorporate the semiconductor element, thereby manufacturing a cavity-filled semiconductor device.

[0158]

Example 30 Using the above resin composition for semiconductor encapsulation α,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board and both were electrically connected by a bonding wire was prepared. Then, the semiconductor device is heated to 70 ° C.
Was heated and applied by printing through the opening of the mask. After that, 150 ℃ × 3
A cavity-fill type semiconductor device was manufactured by forming a sealing resin layer so as to incorporate a semiconductor element by heating and curing in a time.

[0159]

Example 31 Using the semiconductor encapsulating resin composition α,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board and both were electrically connected by a bonding wire was prepared. Then, the semiconductor device is heated to 70 ° C.
Semiconductor encapsulation resin composition α heated to 5 Torr
It was applied by printing through the opening of the mask under vacuum. Thereafter, the semiconductor device was cured by heating at 150 ° C. for 3 hours to form a sealing resin layer so as to incorporate the semiconductor element, thereby manufacturing a cavity-filled semiconductor device.

[0160]

Example 32 Using the resin composition α for semiconductor encapsulation,
A semiconductor device was manufactured as follows. That is, a device in which a semiconductor element was mounted on a printed circuit board and both were electrically connected by a bonding wire was prepared. Then, the semiconductor device is heated to 70 ° C.
Semiconductor encapsulation resin composition α heated to 5 Torr
It was applied by printing through the opening of the mask under vacuum. Next, the atmosphere pressure was set to 150 Torr, voids in the semiconductor sealing resin composition α were removed, and the semiconductor sealing resin composition heated to 70 ° C. while maintaining the 150 Torr state. Finish printing was performed using α. Thereafter, the semiconductor device was cured by heating at 150 ° C. for 3 hours to form a sealing resin layer so as to incorporate the semiconductor element, thereby manufacturing a cavity-filled semiconductor device.

[0161]

Embodiment 33 On the mounting substrate (motherboard), the semiconductor device manufactured in the above embodiment 20 was mounted, electrically connected and heated to 100 ° C. Then 7
The gap between the mounting substrate and the semiconductor device was filled with the semiconductor sealing resin composition α heated to 0 ° C. using a dispenser. Then, by curing at 150 ° C. for 3 hours, a sealing resin layer was formed in a gap between the semiconductor device and the mounting substrate to manufacture a semiconductor product.

The presence or absence of air bubbles in each of the obtained semiconductor devices and the sealing resin layer of the device in which the semiconductor device was mounted on the mounting substrate was checked visually. The results are shown in Tables 9 to 11 below.

[0163]

[Table 9]

[0164]

[Table 10]

[0165]

[Table 11]

From the results of Tables 9 to 11, the results of Example 2 were obtained.
Except for 8 and 30, most of the sealing resin layers of the semiconductor devices had no air bubbles or only a small amount of air bubbles were observed.

[0167]

As described above, the present invention provides a liquid epoxy resin (component A), a solid phenol resin (component B),
A resin composition for semiconductor encapsulation containing a latent curing accelerator (C component) and an inorganic filler (D component),
The viscosity of the resin composition for semiconductor encapsulation at each of 5 ° C. and 80 ° C. is set in a specific range. Therefore, the pot life is longer than that of the conventional liquid sealant, and the storage stability is excellent. In addition, even if it is solid or semi-solid at room temperature, the viscosity is sharply reduced at a temperature as low as about 40 to 80 ° C., and the liquid can be liquefied. In addition, since the resin composition for semiconductor encapsulation of the present invention can be stored in a solid or semi-solid state at room temperature, the inorganic filler (D component) does not settle. Therefore, it can be stored in a solid or semi-solid state, and then liquefied at a low temperature if necessary, so that it can be used for good sealing. As a result, reliability, particularly, moisture resistance reliability Semiconductor device with high reliability can be obtained.

In particular, the above solid phenolic resin (component B)
Among them, when a polyfunctional solid phenol resin is used, there is an advantage that the glass transition temperature (Tg) increases and the heat resistance increases.

The latent curing accelerator (component C)
When a microcapsule-type curing accelerator having a core / shell structure in which a core portion composed of a curing accelerator is covered with a specific shell portion is used, a resin composition for semiconductor encapsulation containing the same is used. Has a very long pot life,
There is an advantage that storage stability is particularly excellent.

Further, when spherical fused silica is used as the above-mentioned inorganic filler (component D) and is contained at a specific ratio in the entire resin composition for semiconductor encapsulation, the semiconductor containing the same is used. The sealing resin composition has an advantage of being excellent in fluidity and particularly excellent in discharge and application workability.

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Claims (9)

[Claims] 1. A resin composition for encapsulating a semiconductor, comprising the following components (A) to (D), wherein the viscosity of the resin composition for encapsulating a semiconductor is not less than 7000 poise at 25 ° C. and 80 ° C. The resin composition for semiconductor encapsulation is set to 5000 poise or less. (A) Liquid epoxy resin. (B) Solid phenolic resin. (C) Latent curing accelerator. (D) an inorganic filler. 2. The resin composition for semiconductor encapsulation according to claim 1, wherein the solid phenol resin as the component (B) is a polyfunctional solid phenol resin. 3. The core of the latent curing accelerator, which is the component (C), comprising a curing accelerator, has the following general formula (1):
The resin composition for semiconductor encapsulation according to claim 1 or 2, which is a microcapsule-type curing accelerator having a core / shell structure covered with a shell portion containing a polymer having a structural unit represented by the following formula as a main component. Embedded image 4. The inorganic filler as the component (D),
A spherical fused silica powder, wherein the spherical fused silica powder is contained in an amount of 15 to 85% by weight in the whole resin composition for semiconductor encapsulation.
The resin composition for semiconductor encapsulation according to any one of claims 1 to 3, which is contained at a ratio of: 5. A semiconductor in which a semiconductor element is mounted on a printed circuit board via a plurality of connection electrode portions, and a gap between the printed circuit board and the semiconductor element is sealed by a sealing resin layer. 2. The device according to claim 1, wherein said sealing resin layer is formed of a resin.
A semiconductor device formed of the resin composition for semiconductor encapsulation according to any one of claims 4 to 4. 6. A semiconductor in which a semiconductor element is mounted on a printed circuit board via a plurality of connection electrode portions, and a gap between the printed circuit board and the semiconductor element is sealed by a sealing resin layer. A method of manufacturing a device, wherein a gap between the printed circuit board and the semiconductor element is filled with the resin composition for semiconductor encapsulation according to any one of claims 1 to 4, and then cured. A method for manufacturing a semiconductor device, comprising forming the sealing resin layer. 7. A semiconductor element is mounted on the surface of the printed circuit board, and the printed circuit board and the semiconductor element are electrically connected.
A semiconductor device comprising a semiconductor element and a periphery thereof sealed with a sealing resin layer so as to incorporate the semiconductor element, wherein the sealing resin layer is a semiconductor device according to any one of claims 1 to 4. A semiconductor device formed of a sealing resin composition. 8. A semiconductor device is mounted on the surface of the printed circuit board, and the printed circuit board and the semiconductor device are electrically connected.
5. A method of manufacturing a semiconductor device, wherein a periphery of a semiconductor element is sealed with a sealing resin layer so as to incorporate the semiconductor element, wherein the semiconductor element is mounted on a wiring circuit board on a semiconductor element mounting surface side. A method for manufacturing a semiconductor device, comprising supplying the resin composition for semiconductor encapsulation according to any one of the preceding claims and curing the composition to form the encapsulation resin layer. 9. A semiconductor device having a resin sealing layer formed on a mounting substrate via a plurality of connection electrode portions with the wiring circuit board of the semiconductor device facing the semiconductor device. A semiconductor product in which a gap between a substrate and a semiconductor device is sealed with a sealing resin layer, wherein the sealing resin layer is used for semiconductor sealing according to any one of claims 1 to 4. A semiconductor product characterized by being formed of a resin composition.