JP2003002955A - Resin composition for sealing semiconductor and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for sealing a semiconductor having a long pot life, excellent storage stability and excellent out-putting and coating efficiency and a semiconductor device using the resin composition. SOLUTION: This resin composition for sealing the semiconductor device comprises (A) a liquid epoxy resin, (B) a liquid phenol resin and (C) a microcapsule type curing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for semiconductor encapsulation which is excellent in pot life, coating workability and storage stability, and a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, TAB (Tape Automated Bonus)
ding, tape automated bonding), COB
A liquid encapsulant is used for semiconductor encapsulation such as (Chip On Board). The liquid sealant is used at room temperature (25 ° C), dispenser,
By sealing the semiconductor element with resin by printing etc.,
A semiconductor device is manufactured. As such a liquid sealing agent, generally, an epoxy resin composition containing a liquid epoxy resin, a liquid curing agent, and a usual curing accelerator is known. However, since the liquid sealant has a short pot life and poor storage stability, it causes a problem that the viscosity becomes high during the work and the ejection and coating properties are deteriorated.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a long pot life and excellent storage stability, and also has excellent discharge and coating workability for semiconductor encapsulation. An object is to provide a resin composition and a semiconductor device using the same.

[0004]

Means for Solving the Problems That is, the present invention provides (1)
(A) Liquid epoxy resin, (B) Liquid phenol resin,
And (C) a microcapsule type curing accelerator, a resin composition for semiconductor encapsulation containing (2) (C) a microcapsule type curing accelerator, a core portion comprising a curing accelerator,
And the general formula (1) for coating the core part:

[0005]

[Chemical 2]

(Wherein R ₁ and R ₂ are each a hydrogen atom or a monovalent organic group and may be the same or different from each other), and a shell portion containing a polymer having a structural unit The resin composition for semiconductor encapsulation according to (1) above, which has a structure consisting of (3), (3) the liquid phenol resin according to (B) is an allylated phenol resin, according to (1) or (2) above. The present invention relates to a resin composition for semiconductor encapsulation, (4) a semiconductor device encapsulated with the resin composition for semiconductor encapsulation according to any one of (1) to (3) above.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for semiconductor encapsulation of the present invention contains (A) a liquid epoxy resin, (B) a liquid phenol resin, and (C) a microcapsule type curing accelerator. To do.

The liquid epoxy resin is not particularly limited as long as it shows a liquid state at 25 ° C., and various epoxy resins can be used. Here, liquid means
It means the property that the viscosity at 25 ° C. is 50 Pa · s or less.
Examples thereof include bisphenol F type epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, and allylated bisphenol type epoxy resin. These may be used alone or in combination of two or more. The liquid epoxy resin, when used alone, is required to show a liquid state at 25 ° C. However, when two or more kinds are used in combination, not only an individual liquid type but also an individual Include those which do not show a liquid state, but when used in combination, finally show a liquid state at 25 ° C. as an epoxy resin component.

From the viewpoint of curability and fluidity, it is preferable to use a liquid epoxy resin having an epoxy equivalent of 60 to 220 g / eq, and 110 to 200 g / eq.
It is more preferable to use the above.

From the viewpoint of curability and fluidity, the content of the liquid epoxy resin in the resin composition for semiconductor encapsulation of the present invention is preferably 20 to 80% by weight, more preferably 40 to 70% by weight, and 50 to 50% by weight. 60% by weight is particularly preferred.

The liquid phenol resin is not particularly limited as long as it shows a liquid state at 25 ° C., and various phenol resins can be used. Here, the liquid state means a property having a viscosity at 25 ° C. of 50 Pa · s or less. For example, allylated phenol resin, acetylated phenol resin and the like can be mentioned. From the viewpoint of curability and fluidity, an allylated phenol resin is particularly preferable, and specific examples thereof include allylated phenol novolac, diallylated bisphenol A and diallyl bisphenol F. These may be used alone or in combination of two or more. The liquid phenol resin, when used alone, is required to show a liquid state at 25 ° C.
When two or more kinds are used together, not only those which show a liquid state individually but also those which do not show a liquid state individually are those which finally show a liquid state at 25 ° C. as an epoxy resin component when used in combination. Also includes.

From the viewpoint of curability and fluidity, the liquid phenol resin preferably has a hydroxyl equivalent of 30 to 260 g / eq, and more preferably 50 to 200 g / eq.

The content of the liquid phenolic resin in the resin composition for semiconductor encapsulation of the present invention is preferably 20 to 80% by weight, and 30 to 60% by weight from the viewpoint of curability and fluidity.
Is more preferable, and 40 to 50% by weight is particularly preferable.

From the viewpoint of curability and fluidity, the mixing ratio of the liquid epoxy resin and the liquid phenol resin is 0.5 to 1.4 equivalents of the hydroxyl group in the phenol resin per 1 equivalent of the epoxy group in the epoxy resin. It is preferable to blend so that More preferably, it is 0.7 to 1.1 equivalents.

In the combination of the liquid epoxy resin and the liquid phenol resin, for example, it is preferable to use the bisphenol F type epoxy resin and the allylated phenol novolac in combination in terms of fluidity and curability.

The liquid phenol resin acts as a curing agent in the resin composition for semiconductor encapsulation, but as further curing agents, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, etc. An acid anhydride-based curing agent, amines and phthalic acids may be used in combination.

In the present invention, the microcapsule type curing accelerator means fine particles having a core / shell structure in which a core portion made of the curing accelerator is enclosed by a shell portion. Below the curing temperature of the resin composition for semiconductor encapsulation, which is heated during the encapsulation of the semiconductor element, the shell part blocks the physical contact between the core part and the curing agent, so that the resin for semiconductor encapsulation, which occurs during storage Undesired curing of the composition can be suppressed, thereby improving storage stability and prolonging the pot life.

The microcapsule type curing accelerator used in the resin composition for semiconductor encapsulation of the present invention has a viscosity of the resin composition for semiconductor encapsulation containing the same after being left for 30 days in a 25 ° C. atmosphere ( The increase in the measurement temperature: 25 ° C. is suppressed to 10 times or less of the viscosity before measurement (measurement temperature: 25 ° C.). For example, the core part made of various curing accelerators has the following general formula: (1):

[0019]

[Chemical 3]

(Wherein R ₁ and R ₂ are each a hydrogen atom or a monovalent organic group and may be the same or different from each other) are shell parts containing a polymer having a structural unit represented by A microcapsule type curing accelerator having a coated core / shell structure, in which the reactive amino groups present in the shell part are blocked.

In the above-mentioned microcapsule type curing accelerator, the curing accelerator which is the core portion is not particularly limited as long as it has an action of promoting the curing reaction, and a conventional one is used. In this case, from the viewpoint of workability in preparing the microcapsules and the characteristics of the obtained microcapsules, those which are liquid at room temperature are preferable. The liquid at room temperature means that the property of the curing accelerator itself is room temperature (2
In addition to the case where it is liquid at 5 ° C., it includes those which are solid at room temperature and are dissolved or dispersed in an arbitrary organic solvent or the like to be liquid.

Examples of the curing accelerator that is the core include amine-based, imidazole-based, phosphorus-based, boron-based and phosphorus-boron-based curing accelerators. Specifically, alkyl-substituted guanidines such as ethylguanidine, trimethylguanidine, phenylguanidine, and diphenylguanidine, 3- (3,4-dichlorophenyl)-
3-Substituted phenyl-1,1-dimethylureas such as 1,1-dimethylurea, 3-phenyl-1,1-dimethylurea and 3- (4-chlorophenyl) -1,1-dimethylurea, 2-methyl Imidazolines, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline and other imidazolines, 2-aminopyridine and other monoaminopyridines, N, N-dimethyl-N- (2
-Hydroxy-3-allyloxypropyl) amine-N '
-Amine imides such as lactoimide, ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, Organic phosphorus compounds such as tetraphenylphosphonium tetraphenylborate, diazabicycloalkene compounds such as 1,8-diazabicyclo [5.4.0] undecene-7,1,4-diazabicyclo [2.2.2] octane Etc. These may be used alone or in combination of two or more. Among them, the above imidazole compounds and organic phosphorus compounds are preferably used from the viewpoint of easy production of the microcapsule type curing accelerator and easy handling.

The polymer having the structural unit represented by the above general formula (1) in the shell portion can be obtained, for example, by a polyaddition reaction between polyvalent isocyanates and polyvalent amines. Alternatively, it can be obtained by reacting polyisocyanates with water.

The above-mentioned polyisocyanates may be compounds having two or more isocyanate groups in the molecule, and specifically, m-phenylene diisocyanate, p-phenylene diisocyanate, 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
-Phenylene diisothiocyanate, xylylene-1,
Triisocyanates such as 4-diisothiocyanate and ethylidyne diisothiocyanate, tetraisocyanates such as 4,4′-dimethyldiphenylmethane-2,2 ′, 5,5′-tetraisocyanate, hexamethylene diisocyanate and hexane Addition with triol,
Addition product of 2,4-tolylene diisocyanate and brentzcatechol, addition product of tolylene diisocyanate and hexanetriol, addition product of tolylene diisocyanate and trimethylol propane, addition product of xylylene diisocyanate and trimethylol propane, Trimer of aliphatic polyisocyanate such as adduct of hexamethylene diisocyanate and trimethylolpropane, triphenyl dimethylene triisocyanate, tetraphenyl trimethylene tetraisocyanate, pentaphenyl tetramethylene pentaisocyanate, lysine isocyanate, hexamethylene diisocyanate, etc. Examples thereof include isocyanate prepolymers such as the body. These may be used alone or in combination of two or more.

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

On the other hand, the polyvalent amines to be reacted with the polyvalent isocyanates may be compounds having two or more amino groups in the molecule, specifically diethylenetriamine, triethylenetetramine, tetraethylenepenta. 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, spiro acetal type diamine and the like. These may be used alone or in combination of two or more.

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

Further, as the polymer forming the shell portion, for example, polyurethane-polyurea having a urethane bond can also be mentioned by using a polyhydric alcohol together with the above-mentioned polyvalent isocyanates.

The polyhydric alcohol may be aliphatic, aromatic or alicyclic, and is, for example, catechol, resorcinol or 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, xylylenediol, 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 , Hexanetriol, pentaerythritol, glycerin, sorbitol and the like. These alone or 2
Used in combination with more than one species.

Specific examples of R ₁ and R _{2 in} the above general formula (1) include a hydrogen atom or a monovalent organic group such as an alkyl group and an aryl group.

In addition to the polymer having the structural unit represented by the above general formula (1), the shell portion may contain a polymer having a urethane bond, a thermoplastic polymer or the like.

The polymer having the structural unit represented by the general formula (1) is contained in the shell in an amount of preferably 40 to 100% by weight, more preferably 60 to 100% by weight.

The microcapsule type curing accelerator can be produced, for example, by going through the following three steps.

[First Step] A curing accelerator as a core component is dissolved or finely dispersed in a polyisocyanate as a raw material for the shell portion to form an oil phase. Then, the oil phase is dispersed in the form of oil droplets in an aqueous medium (aqueous phase) containing a dispersion stabilizer to prepare an oil phase / water phase type (O / W type) emulsion. Next, in the water phase of the O / W emulsion,
By adding and dissolving the polyvalent amine, the polyvalent amine in the oil phase is interfacially polymerized to cause a polyaddition reaction. Alternatively, by heating the O / W type emulsion, the polyisocyanate in the oil phase reacts with water at the interface with the water phase to generate an amine, and subsequently the self-polyaddition reaction occurs. Thus, a microcapsule dispersion is obtained by producing a microcapsule having a shell portion of a polyurea polymer, preferably a polyurea having the structural unit represented by the general formula (1).

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. Further, this emulsion type is a case where the curing accelerator is lipophilic, and when the curing accelerator has hydrophilicity, it is difficult to form the above emulsion type, but in this case, by adjusting the solubility, O / Interfacial polymerization may be performed as an O (oil phase / oil phase) type emulsion type or an S / O / O (solid phase / oil phase / oil phase) type 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 part. Specifically, in addition to organic solvents such as ethyl acetate, methyl ethyl ketone, acetone, methylene chloride, xylene, toluene and tetrahydrofuran, oils such as phenylxylylethane and dialkylnaphthalene can be used.

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

[Third step] The microcapsule dispersion liquid in which the amino group is blocked with a blocking agent in the second step is
A powdery microcapsule type curing accelerator can be produced by removing excess blocking agent by centrifugation, filtration or the like, and then drying.

In the first step, the aqueous medium (aqueous phase)
As a dispersion stabilizer added to, polyvinyl alcohol, water-soluble polymers such as hydroxymethyl cellulose,
Examples thereof include surfactants such as anionic surfactants, nonionic surfactants, and cationic surfactants. Also, hydrophilic inorganic colloidal substances such as colloidal silica and clay minerals can be used. The addition amount of these dispersion stabilizers is preferably set to 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 reactive with an amino group, and examples thereof include epoxy compounds, aldehyde compounds, acid anhydrides, ester compounds, Examples thereof include compounds that react with an amino group such as an isocyanate compound to form a covalent bond. Furthermore, 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, An acidic compound that forms a salt by a neutralization reaction with an inorganic group such as nitric acid, nitrous acid or hydrochloric acid, or a solid substance having an acidic surface such as silica or aerosil to form a salt. Among these compounds, the above acidic compounds are preferably used as compounds that effectively block the amino groups present on the surface of the shell and inside the shell, and formic acid and organic sulfonic acids are particularly preferably used.

The amount of the blocking agent added is equimolar to the amino groups present on the surface of the shell portion and inside the shell portion. Practically, for example, when using an acidic compound as a blocking agent, preparation of microcapsules (interfacial polymerization)
Immediately after adding an acidic substance (acidic compound) to the dispersion liquid, the pH of the dispersion liquid is adjusted from basic to acidic, preferably pH 2 to 5, and then excess acidic compound is removed by means such as centrifugation or filtration. There is a method of removing.

In the second step, a method of removing unreacted free amine or neutralizing residual amino groups by passing the microcapsule dispersion through an acidic cation exchange resin column is also used.

The average particle size of the microcapsule type curing accelerator is not particularly limited, but for example, from the viewpoint of uniform dispersibility, it is preferably set in the range of 0.05 to 500 μm, and more preferably. Is 0.1 to 30 μm. The shape of the microcapsule type curing accelerator is preferably spherical, but may be elliptical. In the case where the shape of the microcapsules is not a spherical shape, but the particle diameter is not uniformly determined, such as an elliptic shape or a flat shape, a simple average value of the longest diameter and the shortest diameter is taken as the average particle diameter.

Further, in the above-mentioned microcapsule type curing accelerator, the amount of the curing accelerator contained is 10 to 95 of the total amount of the microcapsule in view of reactivity in the curing reaction, isolation of the core portion and mechanical strength. It is preferable to set the content in the range of 30% by weight, particularly preferably 30 to 80% by weight.
Is set to.

From the viewpoint of mechanical strength, the ratio of the thickness of the shell portion to the particle size of the microcapsule type curing accelerator is preferably set to 3 to 25%, and particularly preferably 5 to 25%. Is set.

The amount of the microcapsule type curing accelerator compounded in the resin composition for semiconductor encapsulation is from the viewpoint of the curing rate of the resin composition for semiconductor encapsulation, the liquid phenol resin 100.
It is preferably set to 0.1 to 40 parts by weight (hereinafter abbreviated as “part”). It is particularly preferably 5 to 20 parts.

As the microcapsule type curing accelerator, commercially available microcapsule type curing accelerators may be used in addition to the curing accelerator-containing microcapsules prepared by the above method. Commercially available products include, for example, MCE-9957, a product name of which methyl methacrylate manufactured by Nippon Kayaku Co., Ltd. is used as a shell portion, and Novacure (a product name of HX-3748, 3741, 3742, HX-, manufactured by Asahi Chiba Co., Ltd.).
3921HR, HX-3941HP) and the like.
Further, even if it is a curing accelerator other than the microcapsule type curing accelerator, dicyandiamide, or Fujicure FXR-1030, FXE-1000 manufactured by Fuji Kasei Kogyo Co., Ltd.
It is also possible to use those having weak catalytic activity, such as those having weak catalytic activity, and those having weakened catalytic activity by adding a small amount of a general curing accelerator.

The microcapsule type curing accelerator produced by the above process has a higher density (separation) of the shell portion than the commercially available microcapsule type curing accelerator, so that the core portion does not come into contact with the curing agent with certainty. It is preferable because it can be shut off.

Further, various inorganic fillers can be used in addition to the above components (A) to (C). 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 bismuth may be added.
Among them, spherical silica powder, specifically, spherical fused silica powder is particularly preferably used. Further, those having an average particle diameter of 0.01 to 60 μm are preferable, and those having an average particle diameter of 0.1 to 15 μm are more preferable. In the present invention, the term “spherical” means a flow type particle image analyzer (S
It means that the sphericity measured using YSMEX FPIA-100 type) is 0.85 or more on average.

The content ratio of the inorganic filler is preferably set to be 15 to 85% by weight, and particularly preferably 50 to 80% by weight, based on the whole semiconductor encapsulating resin composition.
Is.

Further, the resin composition for semiconductor encapsulation of the present invention may optionally contain other additives. Examples of such additives include flame retardants, waxes, leveling agents, defoamers, pigments, dyes, silane coupling agents, titanate coupling agents and the like. Examples of the silane coupling agent include γ-
Mercaptopropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyltrimethoxysilane,
γ-methacryloxypropyltrimethoxysilane, amino group-containing silane and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

As the flame retardant, novolac type brominated epoxy resin, brominated bisphenol A type epoxy resin, antimony trioxide, antimony pentoxide, magnesium hydroxide, metal compounds such as aluminum hydroxide, red phosphorus, phosphoric acid ester, etc. The phosphorus compounds and the like can be used, and these can be used alone or in combination of two or more.

Examples of the wax include higher fatty acids, higher fatty acid esters, higher fatty acid calcium, amide compounds, etc., which may be used alone or in combination of two or more.

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

The resin composition for semiconductor encapsulation of the present invention can be manufactured, for example, as follows. That is,
After mixing the above-mentioned components (A) to (C) and, if necessary, other additives, they are kneaded in a heating state in a kneading machine such as a universal stirrer and melt-mixed. Next, set this to room temperature (25
The desired resin composition for semiconductor encapsulation can be produced by cooling at about (° C.). An organic solvent may be added to adjust the fluidity of the resin composition for semiconductor encapsulation. As the organic solvent, for example,
Toluene, xylene, methyl ethyl ketone (MEK),
Examples thereof include acetone and diacetone alcohol. These may be used alone or in combination of two or more.

The viscosity of the resin composition for semiconductor encapsulation of the present invention is measured by RE80U type manufactured by Toki Sangyo Co., Ltd. rotor 3 ° × R.
Using 7.7, the pre-treatment is performed for 1 minute at a cone rotor rotation speed of 1 rpm, and then the value after standing for 10 minutes at 0.1 rpm is measured.

25 ° C. of the resin composition for semiconductor encapsulation of the present invention
The viscosity at 1 to 20 Pa is from the viewpoint of curability and fluidity.
· S is preferable, and 3 to 10 Pa · s is particularly preferable.

Furthermore, the present invention relates to a semiconductor device sealed with the above-mentioned semiconductor sealing resin composition.

The semiconductor device encapsulated with the resin composition for semiconductor encapsulation of the present invention can be manufactured by various conventional methods. For example, flip chip, C
In mounting by OB, graph top, cavity fill, etc., a semiconductor device can be manufactured by potting a resin composition for semiconductor encapsulation using a dispenser and then heating and curing to form an encapsulating resin layer. it can. The above mounting may be performed under vacuum.

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

Side Fill Sealing Method First, a semiconductor device mounted on a printed circuit board via a plurality of connecting electrode portions is prepared. A semiconductor device by flip-chip mounting by injecting and filling the resin composition for semiconductor encapsulation into the gap between the printed circuit board and the semiconductor element using the dispenser, and then heating and curing to form an encapsulating resin layer. Can be manufactured.

The manufacturing of the semiconductor device by the above side fill sealing method may be performed under vacuum. Examples of the apparatus performed under vacuum include model MBC-V series manufactured by Musashi Engineering Co., Ltd. Furthermore, when manufacturing a semiconductor device under the above vacuum, the resin composition for semiconductor encapsulation in a gap between the printed circuit board and the semiconductor element under vacuum,
After injecting and filling with a dispenser, the pressure may be returned to atmospheric pressure and further filled with the resin composition for semiconductor encapsulation to perform differential pressure filling.

Press Bump Sealing Method First, the semiconductor sealing resin composition is potted on a printed circuit board using a dispenser. After that, by a press bump connection method using a flip chip bonder or the like, a semiconductor device by flip chip mounting can be manufactured by forming an encapsulating resin layer at the same time as electrical connection between the semiconductor element and the printed circuit board.

The manufacturing of the semiconductor device by the above-mentioned press bump sealing method may be carried out under vacuum if necessary.

Further, instead of potting using a dispenser, if possible, it is applied by printing and then, by a press bump connection method using a flip chip bonder or the like, simultaneously with the electrical connection between the semiconductor element and the printed circuit board. A sealing resin layer may be formed.

Printing and Sealing Method First, a printed circuit board on which a semiconductor element is mounted via a plurality of connecting electrode portions is prepared. A semiconductor device is manufactured by flip-chip mounting by dropping the semiconductor encapsulating resin composition into a gap between a printed circuit board and a semiconductor element using a dispenser and forming an encapsulating resin layer by printing encapsulation. be able to.

Regarding the printing and sealing, for example, a vacuum printing and sealing device (model VPE-100 series) manufactured by Toray Engineering Co., which utilizes vacuum differential pressure, is used, but it is difficult for bubbles to enter the sealing resin layer. Is preferred.

On the other hand, of the above-mentioned semiconductor device manufacturing methods,
A method of manufacturing the cavity fill type semiconductor device will be specifically described.

First, a semiconductor device mounted on a printed circuit board and electrically connected to each other by a bonding wire or the like is prepared. The heated resin composition for semiconductor encapsulation is potted on a printed circuit board and a semiconductor element by using a dispenser and heat-cured to form an encapsulating resin layer so as to incorporate the semiconductor element, thereby forming a cavity fill. It is possible to manufacture a semiconductor device having a form.

The semiconductor device manufactured by the above sealing method may be manufactured under vacuum. As an apparatus for performing under vacuum, for example, model MBC-V manufactured by Musashi Engineering Co., Ltd.
Series etc. are given.

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

As a 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, for example, flip chip in the method for manufacturing a semiconductor device is used. The same method, side-fill sealing method, press bump sealing method, print sealing method and the like as those described for mounting can be mentioned. ACF (Anisotropic Co) is prepared by dispersing conductive particles of nickel, gold, silver, copper, tin, lead, bismuth, etc. in the resin composition for semiconductor encapsulation.
nductive film), ACP (Anisotropic Conductive P)
It may be used for flip chip mounting as aste). As another usage method, the resin composition for semiconductor encapsulation may be used as a dam material on a wiring circuit board, or may be used as an adhesive and a die bonding agent between the wiring circuit board and the heat dissipation plate.

Production of a semiconductor device using the resin composition for semiconductor encapsulation of the present invention on a semiconductor wafer or a matrix-shaped wiring circuit board can be carried out by various conventional methods.

[0074]

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

[Epoxy resin a1] Bisphenol F type epoxy resin (liquid at 25 ° C .: epoxy equivalent 158 g /
eq).

[Phenol resin bl] Hydroxyl equivalent 135
g / eq allylated phenolic resin (liquid at 25 ° C).

[Microcapsule type curing accelerator cl] A microcapsule type curing accelerator was prepared according to the method described above. That is, first, an adduct 11 of 3 mol of xylylene diisocyanate and 1 mol of trimethylolpropane.
Parts, 4.6 parts of an adduct of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane, were uniformly dissolved in a mixed solution of 7 parts of triphenylphosphine as a curing accelerator and 3.9 parts of ethyl acetate. To prepare an oil phase. In addition, an aqueous phase consisting of 100 parts of distilled water and 5 parts of polyvinyl alcohol was separately prepared, and the oil phase prepared above was added to this and emulsified with a homomixer to obtain an emulsion state,
This was placed in 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 a dropping funnel provided in the above polymerization reactor, added dropwise to the emulsion in the reactor and subjected to interfacial polymerization at 70 ° C. for 3 hours. Then, an aqueous suspension of a microcapsule type curing accelerator was obtained. Then, 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. As a result, a microcapsule type curing accelerator in which the amino groups on the surface and inside the shell were blocked by formic acid was prepared. The microcapsule type curing accelerator thus obtained was separated by centrifugal separation, washed repeatedly with water, and then dried to be isolated as free-flowing powdery particles. The average particle size of the microcapsule type curing accelerator was 2 μm. Moreover, the shell thickness ratio to the particle size of the microcapsules is 15%.
And the total amount of included triphenylphosphine is 30
% By weight.

[Microcapsule type curing accelerator c2] MCE-9957 manufactured by Nippon Kayaku Co., Ltd.

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

Examples 1 and 2 and Comparative Example 1 The above components were blended in the blending ratios shown in Table 1 below, and kneaded in a universal stirrer and melt mixed. Next, the desired resin composition for semiconductor encapsulation was produced by cooling this at room temperature. The kneading conditions are as shown below.

First, an epoxy resin and a phenol resin were charged, mixed for 5 minutes at 60 ° C., a microcapsule type curing accelerator or a curing accelerator was added, and the mixture was mixed for 5 minutes and received.

[0084]

[Table 1]

Test Example 1 With respect to the resin compositions for semiconductor encapsulation of Examples 1 and 2 and Comparative Example 1 thus obtained, each viscosity at 25 ° C. was measured by using an E-type viscometer according to the above-mentioned method. did. Furthermore, storage stability (degree of change in viscosity), discharge and coating workability, and pot life were measured and evaluated according to the following methods. The results are shown in Table 2.

Storage stability: degree of change in viscosity The composition was allowed to stand in an atmosphere of 25 ° C. (30 days), and the viscosity before and after standing was measured using an E-type viscometer (measurement temperature: 25.
C). If the viscosity after standing is 3.0 times or less of the viscosity before standing ◎, if the viscosity after standing is more than 3.0 times and 10 times or less than the viscosity before standing ○, the viscosity after standing Those having a viscosity of more than 10 times the previous viscosity were marked with x.

The pot life, the dischargeability, and the coating workability The semiconductor encapsulating resin composition adjusted to 25 ° C. was evaluated by the discharge amount when it was discharged under constant conditions of time and pressure using a dispenser. That is, 10 cc syringe by Musashi Engineering Co., Ltd., metal needle (inner diameter 0.7 mm)
And the discharge amount after 10 seconds at a pressure of 0.2 MPa is 50 ° C.
It was measured before and after standing for × 24 hours. As a result, those with a difference in discharge amount after 24 hours of 10% or less were rated as ⊚, those with a difference of 30% or less as ◯, and those exceeding 30% as x.

[0088]

[Table 2]

From the results of Table 2 above, Examples 1 and 2 were obtained.
It can be seen that, as compared with Comparative Example 1, the pot life is long, the storage stability is excellent, and the coating and coating workability is excellent. In particular, Example 1 has a very long pot life as compared with the one using a commercially available microcapsule type curing accelerator,
Especially excellent in storage stability. This is because the microcapsule type curing accelerator comprising the shell portion having the structural unit represented by the general formula (1) is used, and therefore the curing accelerator is excellent in isolation.

[0090]

According to the present invention, there is provided a resin composition for encapsulating a semiconductor, which has a long pot life, is excellent in storage stability, and is excellent in discharge and coating workability. Furthermore, a semiconductor device sealed with the resin composition for semiconductor sealing is provided.

Claims (4)

[Claims] 1. A resin composition for semiconductor encapsulation, comprising (A) a liquid epoxy resin, (B) a liquid phenol resin, and (C) a microcapsule type curing accelerator. 2. A microcapsule type curing accelerator (C), which comprises a core portion comprising the curing accelerator, and a general formula (1): (Wherein R ₁ and R ₂ are each a hydrogen atom or a monovalent organic group, and may be the same or different from each other), and a structure comprising a shell portion containing a polymer having a structural unit represented by The resin composition for semiconductor encapsulation according to claim 1, which comprises: 3. The resin composition for semiconductor encapsulation according to claim 1, wherein the liquid phenol resin (B) is an allylated phenol resin. 4. A semiconductor device encapsulated with the semiconductor encapsulating resin composition according to claim 1.