JP2003040980A - Resin composition for semiconductor sealing and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black pigment resin composition for semiconductor sealing which has good dispersibility to a resin for semiconductor sealing substituted for a carbon black without recohesion in curing and a semiconductor device using the composition. SOLUTION: The composition containing (A) an epoxy resin, (B) a curing agent, (C) a curing promoter and (D) a masterbatch of the curing agent an black titanium oxide and the device using the composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for semiconductor encapsulation, which contains a specific black pigment, has good dispersibility of the pigment, does not re-aggregate upon curing, and is excellent in storage stability. And a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, TAB (Tape Auto) has been used.
mated Bonding, Tape Automated Bonding), COB (Chip On Boar)
d, chip-on-board), flip-chip, wafer level CSP, etc. For semiconductor encapsulation, a semiconductor device is usually resin-encapsulated by dispenser, printing, transfer molding, etc. and cured at 150-180 ° C. Manufactured. As such a sealing agent, an epoxy resin composition containing an epoxy resin, a curing agent, an ordinary curing accelerator, and carbon black is generally known.

[0003]

However, since carbon black is difficult to disperse in the resin composition for semiconductor encapsulation, it is used in a semiconductor element provided with a protruding electrode portion such as a flip chip or a wafer level CSP. In this case, there is a problem that carbon is clogged between the wiring pitches to cause a short circuit, or when it is used as an underfill agent, it cannot be filled in the interface between the semiconductor element and the wiring board.
Even if the carbon is premixed with a part of the resin composition to improve the dispersibility, the same problem occurs because the carbon agglomerates again during curing. At present, the distance between the protruding electrodes is short, which is on the order of several tens of μm, and is expected to reach 10 μm in the future. Further, the gap between the flip chip and the wiring substrate is currently 50 to 100 μm, and is expected to be 20 μm in the future. At present, carbon particles having a size of 50 microns or more are present after curing.

The present invention has been made in view of the above circumstances, and has a good dispersibility in a resin for encapsulating a semiconductor instead of carbon black, and a black pigment-based semiconductor encapsulation that does not cause re-aggregation during curing. A resin composition for use and a semiconductor device using the same are provided.

[0005]

The present inventors have conducted a series of studies in order to obtain a composition in which the black pigment contained therein has good dispersion with the encapsulating resin and does not re-aggregate during curing. As a result, they have found that the intended purpose can be achieved by using an epoxy resin, a curing agent, a curing accelerator, and a masterbatch of a black titanium oxide with a curing agent, and have completed the present invention.

In particular, a microcapsule type curing accelerator is used as the curing accelerator, and the microcapsule type curing accelerator has a core / shell structure in which a core portion made of the curing accelerator is covered with a specific shell portion. When it is one, the resin composition for semiconductor encapsulation containing the microcapsule type curing accelerator has a very long pot life,
It has been found that it has the advantage of being particularly excellent in storage stability.

That is, according to the present invention, the following (A) to (D) components (A) epoxy resin, (B) curing agent, (C) curing accelerator, (D) curing agent and black titanium oxide are used. A resin composition for semiconductor encapsulation containing the master batch of, preferably component (D) is a filler master batch in which black titanium oxide is dispersed in a phenolic curing agent with a particle size of 10 μm or less, Black titanium oxide is a mixture of compounds represented by the general formula Ti _W O _X (1) (where W represents an integer of 1 to 3 and X represents a number of 1.0 to 7.0). It is a certain black titanium oxide, the phenolic curing agent is solid at 25 ° C., the hydroxyl group equivalent of 60 to 250 g / eq, 50 to 12
It has a softening point of 0 ° C. and a melting point of 45 to 250 ° C., and the amount of the black titanium oxide and the phenol curing agent is 5 to 70% by weight with respect to the total amount of the phenol curing agent and the black titanium oxide. % And 95 to 30% by weight, a resin composition for semiconductor encapsulation, which is a masterbatch of a phenolic curing agent and black titanium oxide, is the first gist.

A second aspect of the present invention is a semiconductor device obtained by encapsulating a semiconductor element with the above-mentioned resin composition for encapsulating a semiconductor.

In a preferred embodiment of the semiconductor device, a semiconductor element is mounted on a wiring circuit board via a plurality of connecting electrode portions, and a space between the wiring circuit board and the semiconductor element is A semiconductor device encapsulated with the resin composition for semiconductor encapsulation according to the first aspect of the invention.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described in detail.

The semiconductor encapsulating resin composition of the present invention is
It is obtained using a masterbatch of (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) curing agent and black titanium oxide.

In the present invention, the epoxy resin as the component (A) may be solid or liquid at room temperature, and various epoxy resins can be used. For example, bisphenol F type epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin,
Examples thereof include allylated bisphenol type epoxy multifunctional epoxy resins. These may be used alone or in combination of two or more. Of these, it is preferable to use an epoxy resin which is liquid at room temperature in consideration of dispersibility when compounded with other components.

As the liquid epoxy resin,
It is preferable to use one having an epoxy equivalent of 110 to 220 g / eq, and especially an epoxy equivalent of 140 to 20.
It is preferable to use 0 g / eq.

The curing agent as the component (B) in the present invention is not particularly limited, and various phenolic curing agents, acid anhydrides, amines, phthalic acids and the like can be used. For example, allylated phenol novolac, diallylated bisphenol A, acetylated phenol, diallyl bisphenol F, phenol novolac, polyfunctional phenol, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride and the like can be mentioned. These may be used alone or in combination of two or more. Among the above curing agents, as the phenolic curing agent and the acid anhydride, those having a hydroxyl group equivalent and an acid anhydride equivalent of 30 to 260 g / eq are preferable, and among them, those having a hydroxyl group equivalent of 50 to 200 g / eq are used. Is preferred.

The mixing ratio of the epoxy resin and the curing agent is such that the amount of the hydroxyl group or the acid anhydride group in the phenolic curing agent is 0.5 to 1 equivalent of the epoxy group in the epoxy resin.
It is preferable that the compounding amount be 1.4 equivalent. More preferably, it is 0.7 to 1.1 equivalents.

In the present invention, it is preferable to use a bisphenol F type liquid epoxy resin in combination with a phenol novolac resin in combination with the above epoxy resin and a curing agent from the viewpoint of fluidity and curability.

As the curing accelerator as the component (C) in the present invention, those known per se can be used, and are not particularly limited. However, in order to extend the pot life of the obtained resin composition for semiconductor encapsulation and improve the storage stability, it is preferable to use a latent curing accelerator as a curing agent.

The latent curing accelerator typically includes a microcapsule type curing accelerator. Such a microcapsule type curing accelerator is contained in a resin composition for semiconductor encapsulation. It is preferable that the viscosity after thickening after standing for 72 hours in an atmosphere of 50 ° C. is 10 times or less than the viscosity before standing. Specific examples thereof include those having a core / shell structure in which a core portion made of various curing accelerators is covered with a shell portion, and the core portion includes a polymer containing a structural unit represented by the following general formula (1). The main component is coalescence. Further, by blocking the reactive amino group present in the shell portion, the resin composition for semiconductor encapsulation containing the same has a very long pot life and is particularly excellent in storage stability. become. Even if a small amount of a usual curing accelerator is used, if the viscosity after thickening is 10 times or less, usually 1 to 3 times (excluding 1), the viscosity before standing. Considered as a latent curing accelerator.

[0019] (However, R ₁ and R ₂ are both hydrogen atoms or monovalent organic groups, and may be the same or different from each other.)

In the above-mentioned microcapsule type curing accelerator, the curing accelerator contained as the core portion is not particularly limited as long as it has the action of promoting the curing reaction, and conventionally known ones can be used. . And
In this case, from the viewpoint of workability when preparing the microcapsules and the characteristics of the obtained microcapsules, those which are liquid at room temperature are preferable. The term "liquid at room temperature" means that the property of the curing accelerator itself is liquid at room temperature (25 ° C), and even if it is a solid at room temperature, it is dissolved or dispersed in any organic solvent or the like to be liquid. Is also included.

Examples of the curing accelerator included as the core portion 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) -1,1-dimethylurea, 3-phenyl-
1,1-dimethylurea, 3- (4-chlorophenyl)-
3-Substituted phenyl-1,1-dimethylurea, etc.
Dimethylureas; 2-methylimidazolines, 2-phenylimidazolines, 2-undecylimidazolines, 2-heptadecylimidazolines and other imidazolines; 2-aminopyridines and other monoaminopyridines; N, N-dimethyl-N- ( 2-hydroxy-3-allyloxypropyl)
Amine imides such as amine-N'-lactoimide; ethyl phosphine, propyl phosphine, butyl phosphine, phenyl phosphine, trimethyl phosphine, triethyl phosphine, tributyl phosphine, trioctyl phosphine, triphenyl phosphine, tricyclohexyl phosphine, triphenyl phosphine / tri Organophosphorus compounds such as phenylborane complex and tetraphenylphosphonium tetraphenylborate; diaza such as 1,8-diazabicyclo [5,4,0] undecene-7,1,4-diazabicyclo [2,2,2] octane Bicycloalkene compounds; and the like. These may be used alone or in combination of two or more. Among them, the imidazole-based compounds and organic phosphorus-based compounds are preferably used from the viewpoint of easy production of the curing accelerator-containing microcapsules and ease of handling.

The shell part containing a polymer having the structural unit represented by the above formula (1) as a main component can be obtained, for example, by a polyaddition reaction between a polyvalent isocyanate and a polyvalent amine. 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'-biphenyldiisocyanate,
3,3'-dimethylphenylmethane-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-1,4
-Diisocyanates such as diisocyanates; triisocyanates such as p-phenylene diisothiocyanate, xylylene-1,4-diisothiocyanate and ethylidyne diisothiocyanate; 4,4'-dimethyldiphenylmethane-2,2 ', 5 Tetraisocyanates such as 5'-tetraisocyanate; an adduct of hexamethylene diisocyanate and hexanetriol, 2,4-
Addition product of tolylene diisocyanate and prenzcatechol, addition product of tolylene diisocyanate and hexanetriol, addition product of tolylene diisocyanate and trimethylol propane, addition product of xylylene diisocyanate and trimethylol propane, hexamethylene diisocyanate and tri Isocyanate prepolymer such as trimer of aliphatic polyisocyanate such as adduct of methylolpropane, triphenyldimethylenetriisocyanate, tetraphenyltrimethylenetetraisocyanate, pentaphenyltetramethylenepentisocyanate, lysine isocyanate, hexamethylenediisocyanate Etc. 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 tolylenediisocyanate and trimethylolpropane and an adduct of xylylenediisocyanate and trimethylolpropane. It is 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 whose main component is a polymer having the structural unit represented by the general formula (1) is formed.

Further, examples of the polymer forming the shell portion (wall film) include polyurethane-polyurea having a urethane bond, which is obtained by using a polyhydric alcohol together with the polyvalent isocyanate. .

The above-mentioned 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, hexane Examples include triol, pentaerythritol, glycerin, sorbitol and the like. These alone or 2
Used in combination with more than one species.

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

[First Step] A hardening accelerator as a core component is dissolved or finely dispersed in a polyisocyanate 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 water phase of the O / W type emulsion,
Interfacial polymerization with the polyisocyanate in the oil phase causes 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 produce an amine, and subsequently causes a self-polyaddition reaction. Thus, the polyurea-based polymer, preferably the polyurea having the structural unit represented by the general formula (1), is used as the shell part (wall film).
A microcapsule dispersion liquid is obtained by producing the microcapsule having

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 into the above emulsion type, but in this case, by adjusting the solubility, an O / O (oil phase / oil phase) emulsion type or S / O / O (solid phase / oil phase / oil phase) emulsion type may be used for interfacial polymerization.

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 (wall film).
Specifically, in addition to organic solvents such as ethyl acetate, methyl ethyl ketone, acetone, methylene chloride, xylene, toluene, tetrahydrofuran, phenylxylylethane,
Oils such as 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.

First, in the first step, as the dispersion stabilizer to be added to the aqueous medium (aqueous phase), water-soluble polymers such as polyvinyl alcohol and hydroxymethyl cellulose, anionic surfactants and nonionic surfactants are used. Agent,
Examples thereof include surfactants such as 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 and esters. Examples thereof include compounds that react with an amino group such as a compound and 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,
p-toluenesulfonic acid, 2-naphthalenesulfonic acid,
Neutralization reaction with organic sulfonic acids such as dodecylbenzene sulfonic acid, phenolic compounds, inorganic acids such as boric acid, phosphoric acid, nitric acid, nitrous acid, hydrochloric acid, etc., and amino groups such as silica, aerosil etc. An acidic compound which forms a salt can be mentioned. Among these compounds, the acidic compound is preferably used as a compound that effectively blocks amino groups present on the surface of the wall film and inside the wall film, and formic acid and organic sulfonic acids are particularly preferably used.

As for the amount of the blocking agent added, the same amount of the blocking agent as the amino groups present on the surface of the wall film and inside the wall film are added. Practically, for example, when an acidic compound is used as the blocking agent, the acidic substance (acidic compound) is added to the dispersion liquid immediately after preparation of the microcapsules (interfacial polymerization).
Is added to adjust the pH of the dispersion liquid from basic to acidic, preferably pH 2 to 5, and then excess acidic compound is removed 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 a second step, the microcapsule dispersion is passed through an acidic cation exchange resin column to remove unreacted free amine. It is also possible to use a method of removing the residual group or neutralizing the residual amino group.

The average particle size of the obtained 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, more preferably 0.1 to 3
It is 0 μm. The shape of the microcapsule type curing accelerator is preferably spherical, but may be elliptical. When the particle size of the microcapsules is not a spherical shape but an elliptical shape, a flat shape, or the like, and the particle diameter is not uniformly determined, the 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 incorporated is preferably set to 10 to 95% by weight, and particularly preferably 30 to 80% by weight based on the total amount of the microcapsules. . That is, when the content of the curing accelerator is less than 10% by weight, the curing reaction takes too long and the reactivity becomes poor. On the contrary, when the content of the curing accelerator exceeds 95% by weight, the thickness of the wall film is increased. Is too thin, and the core (curing agent) isolation and mechanical strength may be poor.

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
It is 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 (share) applied in the kneading step during the production of the epoxy resin composition,
Further, if it exceeds 25%, the release of the included curing accelerator tends to be insufficient.

The compounding amount of the microcapsule type curing accelerator is 100 parts by weight of the curing agent (hereinafter referred to as "part").
It is preferable to set 0.1 to 40 parts. It is particularly preferably 5 to 20 parts. That is, if the compounding amount of the latent curing accelerator is less than 0.1 part, the curing speed is too slow to cause reduction in strength, and if it exceeds 40 parts, the curing speed is too fast and fluidity may be impaired. Because there is.

In the present invention, as the microcapsule type curing accelerator which is the component (C), a commercially available microcapsule type curing accelerator other than the above-mentioned curing accelerator-containing microcapsules can be used as long as the intended purpose is not impaired. Agents can be used. Examples of commercially available products include, for example, product name MCE
-9957 (manufactured by Nippon Kayaku Co., Ltd., which uses methyl methacrylate as a wall film), Asahi Ciba Novacure (trade name HX-3748, 3741, 3742, H
X-3921HR, HX-3941HP) and the like. Further, even if a latent curing accelerator other than the microcapsule type curing accelerator, dicyandiamide, or Fujicure FXR-1030 or FXE manufactured by Fuji Kasei Kogyo Co., Ltd.
It may be one having a weak catalytic activity such as -1000, or one having a weak catalytic activity by adding a small amount of a general curing accelerator.

As the black titanium oxide used in the hardener black titanium oxide masterbatch which is the component (D) of the present invention, any black titanium oxide may be used as long as it is of the general formula Ti _W O. _X (1) (W represents an integer of 1 to 3, and X is 1.0 to 7.0.
A black titanium oxide, which is a mixture of compounds represented by the formula (1), is preferably used. In addition, the black titanium oxide is powdery, and has a powdery property of having a primary average particle diameter of 0.03 to 0.5 nm by an electron microscope and a specific surface area of 20 to 60 m ² / g. Oil absorption is 30-4
Those in the range of 0 ml / 100 g are preferable.

Specific chemical formulas are TiO and Ti.
It is preferably composed of a mixture of two or more selected from the group consisting of ₂ O ₃ and Ti ₃ O ₅ . Especially TiO
Black titanium oxide, which is a mixture of titanium and Ti ₂ O ₃ , or Ti
Black titanium oxide, which is a mixture of ₃ O ₅ and Ti ₂ O ₃ , is preferable. Furthermore, black titanium oxide, which is a mixture of Ti ₃ O _x (X is a value obtained by X-ray diffraction of the ratio of O to Ti, and represents a number of 5 to 5.2), TiO _x (X
Is a value obtained by TG-DTA of the ratio of O to Ti, and represents a number of 1.0 to 1.5), and black titanium oxide which is a mixture thereof is also suitable.

In the above-mentioned curing agent-based black titanium oxide masterbatch, black titanium oxide was used as the curing agent in an amount of 10 μm.
The particles are preferably dispersed in the following particle size, more preferably 3 μm or less. The particle size of black titanium oxide can be measured by an electron microscope.

The concentration of black titanium oxide in the above-mentioned hardener type black titanium oxide masterbatch is 5 to 70.
It is preferably wt%, more preferably 20 to 5
It is 0% by weight.

Further, in addition to the above-described black titanium oxide, the curing agent-based black titanium oxide masterbatch may be blended with other commonly used fillers such as silica powder.

As the curing agent used in the above curing agent-based black titanium oxide masterbatch, a curing agent solid at 25 ° C. is preferable. As the curing agent, various curing agents can be used, and examples thereof include conventionally known phenol resins, phenol compounds, acid anhydrides, amines and phthalic acids. Among these, it is preferable to use a phenolic curing agent from the viewpoint of easy handling. These curing agents may be used alone or in combination of two or more.

The phenol-based curing agent is not particularly limited as long as it shows a solid at 25 ° C., and various phenol curing agents can be used.
It preferably has a hydroxyl group equivalent of 0 g / eq, a softening point of 50 to 120 ° C., and a melting point of 45 to 250 ° C.

Specifically, a polyfunctional phenol resin which is solid at 25 ° C. and has a total of 3 or more OH groups in one molecule can be used as a phenol-based curing agent. And trifunctional phenol resin.

These phenolic resins may be used alone or in combination of two or more kinds, but as a final phenolic resin component, they may be used alone or in combination of two or more kinds. It is desirable to show a solid at 25 ° C.

As a method for forming a masterbatch, for example, a method of heating and melting and mixing with various mixers is suitable, but a medium such as alumina, zirconia, titania, glass, and fluorine is used and a curing agent and a black oxide are used. It is even better to mix with titanium. The concentration of titanium oxide is preferably 5 to 70% by weight, more preferably 10 to 30% by weight.

Specifically, the above-mentioned masterbatch in which black titanium oxide is dispersed in a curing agent with a particle size of 10 μm or less is an apparatus equipped with a stirring blade for heating and dispersing a substance to be dispersed by using a medium. And a particle size of 0.1 in a disperser equipped with a device for heating and filtering the obtained dispersion.
~ 4.0 mm media, temperature: 50-250
C., peripheral speed of a stirring blade: 1.6 m / sec or more under the conditions of a hardener and black titanium oxide are melt-dispersed by heat and melt-filtered.

Here, the apparatus for heating and dispersing the substance to be dispersed has a heating means capable of setting the apparatus temperature to the softening point or melting point of the curing agent. The heating temperature is 50 to 250 ° C, preferably 80 to 180 ° C.

This heating / dispersing device comprises a substance to be dispersed,
That is, it has a container containing a curing agent and black titanium oxide, and the material of this container is not particularly limited as long as it is a material that does not corrode with metals such as glass, fluororesin and stainless steel. However, a metal container can be preferably used in terms of heat conductivity.

The structure of the heating dispersion device is not particularly limited as long as the curing agent and the black titanium oxide can be stirred inside the container and the curing agent inside can be heated and melted.
The shape is preferably cylindrical. Close one of the cylinders,
You may stir the inside of the container with a stirring blade while standing upright with the closed part facing down. Also, as a horizontal type, both ends of the cylinder may be closed and a part thereof may be opened to form a circulation type. But,
In this case, a separate dissolution tank and circulation device must be provided. In short, it suffices for the heating dispersion device to be able to disperse the molten curing agent and the black titanium oxide, which is the coloring material, in a desired dispersion state.

The stirring blade preferably has a diameter of 50 to 95% of the inner diameter of the cylindrical container. The peripheral speed of the stirring blade is
It is 1.6 m / sec or more, preferably 1.6 to 140 m / sec. The number of stirring blades may be one, but in order to uniformly stir the medium as the dispersion medium, a plurality of blades may be arranged in series to disperse the curing agent and the black titanium oxide as the coloring material. preferable.

Media particles having a particle size of 0.1 to 4.0 mm, preferably 0.3 to 1.0 mm can be suitably used. In addition, the amount of media used is
It is preferably 30 to 95% by volume, preferably 50 to 90% by volume.

The type of media used is a glass-based, zirconia-based, alumina-based, titania-based inorganic material-based, or Teflon (registered trademark) -based resin-based material, etc., and a media inert to the curing agent and black titanium oxide is used. Preferably. When a glass-based medium is used, it is preferable to use a high-bee type medium which is less likely to be damaged by stirring and has less impurities.

The molten dispersion thus obtained is
Immediately as it is, it is filtered with a preheated filter to remove foreign matters in the dispersion. That is, as an apparatus for heating and filtering the obtained dispersion, the heating temperature is 50 to 25.
A filter-type filtration device capable of setting a temperature of 0 ° C, preferably 80 to 180 ° C can be used. The apparatus may be equipped with such equipment because the filtration speed is increased and efficiency is increased by applying pressure or pressure reduction, mechanical vibration or sonic vibration during filtration.

Here, the openings of the filter used in the filter-type filtration device are preferably 10 μm or less, more preferably 8 μm or less, and further preferably 3 μm.
m or less is used. Further, it is also possible to carry out preliminary filtration with a filter having a large opening in advance and then perform filtration with the above-mentioned filter. The heating temperature of the filter is determined by the softening point and melting point of the curing agent,
It is desirable to set the temperature between 50 and 200 ° C, preferably between 80 and 180 ° C.

When the filter is made of stainless steel, it is 50
Twill weave can be used up to about μm diameter, but the aperture is 10 μm
In the following cases, it is preferable to use stainless steel fibers sintered under high temperature vacuum. For example, Nippon Seisen Co., Ltd. Naslon filter NF-03, NF-0
5, NF-06 and the like can be preferably used. Alternatively, a sintered body of silica or alumina may be used as long as a desired opening is obtained.

In the above heating dispersion device and heating filtration device, since the viscosity of the dispersion changes depending on the temperature and non-uniformity of dispersion occurs, the temperature of the heating dispersion device and the heating filtration device is set to the set temperature. Within ± 4 ℃, preferably ±
It is preferable to control the temperature within 2 ° C, more preferably within ± 1 ° C.

As a heating means in the heating dispersion device and the heating filtration device, an electric furnace, a band heater, a heating medium circulation type heating device, a surface heating element and the like are preferable. For the above reason, it is preferable to use a temperature control device that can control the temperature in the set temperature by ± 2 ° C, preferably ± 1 ° C. Furthermore, when a temperature difference occurs between the upper and lower heat generating regions, it is preferable to divide and heat the upper and lower parts separately. The heating temperature is set in the range of 50 to 250 ° C. depending on the softening point and melting point of the curing agent.
It is preferable to set the temperature between 0 and 180 ° C.

The dispersion after filtration is granulated or pulverized to prepare a masterbatch for easy use. In the case of the granulation method, the molten liquid after filtration is dropped from a nozzle, brought into contact with cold air or a cooling plate to be solidified, and granulated into predetermined particles. In the case of the crushing method, the melt after filtration is cooled to room temperature to form a block, and the block is crushed to a desired size.
For crushing, a known crusher can be used if no foreign matter is mixed. For example, a household electric mixer can be used for a small scale, and a power mill manufactured by Dalton Co., Ltd. can be used for a large scale. When the crushed particle size is 4 mm or less, preferably 2 mm or less, it is easy to mix with an epoxy resin or the like.

Further, the resin composition for semiconductor encapsulation of the present invention may optionally contain other additives in addition to the above essential components. Examples of other additives include inorganic fillers, flame retardants, waxes, leveling agents, defoamers, pigments, dyes, silane coupling agents, titanate coupling agents, and the like.

Examples of the inorganic fillers include silica, clay, gypsum, calcium carbonate, barium sulfate, alumina oxide, beryllium oxide, silicon carbide, silicon nitride and aerosil, but nickel, gold, copper, silver and tin. ,
Conductive particles such as lead and bismuth may be added. Among them, spherical silica powder, specifically, spherical fused silica powder is particularly preferably used. Furthermore, the average particle size is 0.01
It is preferably in the range of -60 μm, more preferably in the range of 0.1-15 μm. In the present specification, the term “spherical” means a flow type particle image analyzer (SYS).
It means that the sphericity measured using MEX FPIA-100 type) is 0.85 or more on average.

As the silane coupling agent, for example,
γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
Examples thereof include amino group-containing silanes, which may be used alone or in combination of two or more.

Examples of the flame retardant include 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 and phosphate ester. Phosphorus compounds and the like are listed, and these may be used alone or in combination of two or more.

Examples of the waxes include higher fatty acids, higher fatty acid esters, higher fatty acid calcium, amide compounds and the like, and they may be used alone or in combination of two or more.

In addition to the above-mentioned other additives, the resin composition for semiconductor encapsulation of the present invention is blended with components such as silicone oil, silicone rubber, synthetic rubber, and reactive diluent to reduce stress ( An ion trap agent such as hydrotalcite or bismuth hydroxide may be added for the purpose of stress dispersion) or for improving reliability in a 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 D and, if necessary, other additives, they are kneaded in a kneading machine such as a universal stirrer in a heated state and melt-mixed. Next, the desired resin composition for semiconductor encapsulation can be produced by cooling it at room temperature (about 25 ° C.). 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 production of a semiconductor device using the resin composition for semiconductor encapsulation of the present invention can be carried out by various conventionally known methods. For example, in mounting by flip chip, COB, graph top, cavity fill, etc., the resin composition for semiconductor encapsulation is potted using a dispenser and then heated and cured to form an encapsulation resin layer. A semiconductor device can be manufactured. The above mounting may be performed under vacuum.

The flip-chip mounting of the above-described semiconductor device manufacturing methods 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 Encapsulation Method] First, a semiconductor device mounted on a printed circuit board via a plurality of connecting electrode portions is prepared. Then, the resin composition for semiconductor encapsulation is injected into the gap between the printed circuit board and the semiconductor element by using a dispenser, and then filled, and then heated and cured to form an encapsulation resin layer. A semiconductor device can be manufactured.

The semiconductor device manufactured by the 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. Further, when manufacturing a semiconductor device under the above vacuum, after filling and filling the gap between the wiring circuit board and the semiconductor element with a resin composition for semiconductor encapsulation using a dispenser under a vacuum, and further returning to atmospheric pressure Differential pressure filling may be performed by filling the semiconductor sealing resin composition.

[Press Bump Sealing Method] First, the semiconductor sealing resin composition is potted on a printed circuit board using a dispenser. At that time, 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.

The semiconductor device may be manufactured by the above-mentioned press bump sealing method under vacuum if necessary.

Further, instead of potting using a dispenser, if possible, coating is performed by printing, and then, by a press bump connection method using a flip chip bonder or the like, the electrical connection between the semiconductor element and the printed circuit board is performed simultaneously. 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. Then, the resin composition for semiconductor encapsulation is dropped into a gap between the printed circuit board and the semiconductor element by using a dispenser, and a sealing resin layer is formed by printing encapsulation to manufacture a semiconductor device by flip chip mounting. can do.

For the above-mentioned printing and sealing, a vacuum printing and sealing device (model VPE-100 series) manufactured by Toray Engineering Co., which utilizes vacuum differential pressure, is used, since it is difficult for bubbles to enter the sealing resin layer. preferable.

On the other hand, of the methods of manufacturing a semiconductor device, a method of manufacturing a semiconductor device having a cavity fill form 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. Then, the heated resin composition for semiconductor encapsulation is potted on the printed circuit board and the 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. It is possible to manufacture a fill type semiconductor device.

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 for heat-curing the resin composition for encapsulating a semiconductor 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, the flip method in the method of manufacturing a semiconductor device is used. The same method, side fill sealing method, press bump sealing method, print sealing method, etc. as described for chip mounting can be mentioned. In addition, in the above resin composition for semiconductor encapsulation, nickel, gold, silver, copper, tin,
Conductive particles such as lead and bismuth are dispersed, and ACF (An
isotropic Conductive Fil
m), ACP (Anisotropic Conduc)
It may be used for flip chip mounting as a "Tive Paste". As another method of use, the resin composition for semiconductor encapsulation may be used as a dam material on a printed circuit board, or may be used as an adhesive or a die bond agent between the printed 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 conventionally known methods.

[0089]

EXAMPLES Next, examples will be described together with comparative examples.

(1) Examples and comparative examples of the resin composition for semiconductor encapsulation of the present invention will be described. First, the following components were prepared prior to the examples.

[Epoxy Resin a1] A crystalline epoxy resin represented by the following structural formula (2) was used. (Epoxy equivalent: 174
(g / eq, melting point 79 ° C)

[0092]

[Epoxy resin a2] Bisphenol F type epoxy resin (liquid at 25 ° C .: epoxy equivalent 158 g /
eq)

[Phenolic curing agent b1] A mixture of a trifunctional phenol curing agent represented by the following chemical formula (3) and a tetrafunctional phenol curing agent represented by the chemical formula (4) (melting point 132 ° C., Hydroxyl equivalent 87 g / eq). The peak area ratio (area ratio to the total peak area) of the liquid chromatographic analysis is about 65% in the formula (3) and about 35% in the formula (4).

[0095]

[0096]

[Curing accelerator c1] A microcapsule type curing accelerator was prepared according to the method described above. First, 11 parts of an adduct of 3 mol of xylylene diisocyanate and 1 mol of trimethylolpropane, and 3 parts of an adduct of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane.
6 parts of triphenylphosphine 7 as a curing accelerator
Part and 3.9 parts of ethyl acetate were uniformly dissolved 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 to emulsify with a homomixer to obtain an emulsion state, which was refluxed with a stirrer, It was charged into a polymerization reactor equipped with 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 the suspension to adjust the pH of the system to 3. Thus, a microcapsule type curing accelerator in which the amino groups on the surface of the wall film and inside were blocked with formic acid was prepared. The microcapsule type curing accelerator thus obtained is separated by centrifugation,
After washing with water repeatedly, it was dried to isolate as free-flowing powdery particles. The average particle size of the microcapsule type curing accelerator was 2 μm. Also,
The ratio of shell thickness to particle size of microcapsules is 15
%, And the inclusion amount of triphenylphosphine is 3% of the total.
It was 0% by weight.

[Curing Accelerator c2] 2-Ethyl-4-ethylimidazole (Curezol 2E manufactured by Shikoku Chemicals Co., Ltd.
4MZ).

[Hardening Agent-Based Black Titanium Oxide Masterbatch d1] A masterbatch of the above-mentioned b1 phenol resin and black titanium oxide.

Titanium oxide used: Reddish black powder obtained by heating titanium powder (Ti) and titanium oxide (TiO ₂ ) in vacuum at 1600 ° C. until blackness becomes constant, and X Line analysis mainly consists of TiO and Ti ₂ O ₃ , and TG
-Titanium oxide which is TiO _1.33 from DTA analysis.

Manufacturing method: Phenolic resin (15% by weight)
, Black titanium oxide (6% by weight) and 1 mm zirconia beads (79% by weight), inner diameter 40 mm, height 15
cm in a stainless steel container, heated to 150 ° C., melted, stirred and dispersed for 2 hours at a peripheral speed of a stirring blade (diameter of 35 mm) of 2.2 m / sec, and preheated to remove beads with stainless steel having an opening of 150 μm. Then, 120 ° C. equipped with a stainless steel filter NF-06 manufactured by Nippon Seisen Co., Ltd. having an opening of 5 μm.
The mixture was placed in a heating / pressurizing filtration device heated to 1, and the temperature was sufficiently raised to a predetermined temperature.

[Hardening Agent-Based Black Titanium Oxide Masterbatch d2] A masterbatch of the b1 phenol resin and black titanium oxide.

Titanium oxide used: titanium chloride (TiC
is a bluish black powder obtained by reacting at 1000 ° C. in a mixed gas of 1 ₂ ) and hydrogen (H ₂ ), and is mainly composed of Ti ₃ O ₄ and Ti ₄ O ₇ by X-ray diffraction. titanium oxide is Ti ₃ O _4.02 from -DTA analysis.

Manufacturing method: The mixing ratio of the phenol resin and titanium oxide and the manufacturing method of the masterbatch are the same as those of d1.

[Hardening Agent-Based Black Titanium Oxide Masterbatch d3] A masterbatch of the phenol resin b1 and carbon black 3030 manufactured by Mitsubishi Chemical Corporation.

Characteristics of carbon: The carbon has a specific surface area of 22 m ² / g by nitrogen adsorption, a DBP oil absorption of 73 ml / 100 g, and a primary particle diameter of 85 nm.

Manufacturing method: The compounding ratio of the phenol resin and carbon and the manufacturing method of the masterbatch are the same as those of d1.

Examples 1 to 3 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, a phenol-based curing agent, a curing agent-based titanium oxide masterbatch or a carbon masterbatch was charged and mixed at 150 ° C. for 5 minutes, then the temperature was lowered to 60 ° C. and a curing accelerator was added for 5 minutes. Mixed and accepted.

With respect to the resin compositions for encapsulating semiconductors of Examples and Comparative Examples thus obtained, storage stability (degree of change in viscosity), titanium oxide and carbon before and after curing of the semiconductor resin composition Was evaluated for dispersibility.

[Storage Stability] (Degree of Change in Viscosity) The composition was left in an atmosphere of 25 ° C. (30 days), and the viscosity before and after the standing was measured using an E-type viscometer (measurement temperature: 70 ° C.). When the viscosity after standing is 1.5 times or less of the viscosity before standing ◎, when the viscosity after standing is more than 1.5 times and 3.0 times or less of the viscosity before standing ○, after standing The viscosity was marked with Δ when the viscosity was more than 3.0 times and less than 10 times the viscosity before standing, and was marked with X when the viscosity after standing was more than 10 times the viscosity before standing.

[Dispersibility of Titanium Oxide in Uncured Semiconductor Resin Composition] The prepared resin composition is placed on a glass plate having a thickness of 1 mm in an amount of about 5 to 50 mg, and 0.15 mm from the top.
It was sandwiched between the glass plates and heat treated in a dryer at 70 ° C. for 15 minutes to spread the resin thinly. Then, the particle size of titanium oxide or carbon black in the resin composition was measured with an optical microscope.

When 15 μm or more is present in the visual field, it cannot be used ×, 10 to 15 μm is Δ, 5 to 10 μm is ◯, 5 μ
m or less was marked as ◎.

[Dispersibility of Titanium Oxide in Cured Semiconductor Resin Composition] Evaluation sample prepared in the same manner as above was used for 175
After heat treatment at 15 ° C. for 15 minutes, the particle size of titanium oxide or carbon was measured with an optical microscope.

When 15 μm or more exists in the visual field, it cannot be used ×, 10 to 15 μm is Δ, 5 to 10 μm is ◯, 5 μ
m or less was marked as ◎.

[0118]

[Table 1]

From the results shown in Table 1, it can be seen that all the products of Examples have better storage stability and excellent dispersibility of titanium oxide, as compared with the products of Comparative Examples (conventional examples). Further, it can be seen that the particle diameters of titanium oxide before and after curing are the same and reaggregation does not occur during curing. With a semiconductor device using such a semiconductor encapsulant, pigment particles do not become clogged between the protruding electrodes, and a highly reliable semiconductor device can be obtained.

On the other hand, it can be seen that the comparative products have poor carbon dispersibility before curing, the particle size is further increased after curing, and re-aggregation occurs during curing.

[0121]

According to the present invention, a resin composition for semiconductor encapsulation having good storage stability and dispersibility of titanium oxide in which reaggregation does not occur during curing can be obtained. Further according to the invention,
Pigment particles are not clogged between the protruding electrodes, and a highly reliable semiconductor device can be obtained.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/31 F term (reference) 4F070 AA44 AA46 AB10 AC15 AC37 AE01 AE04 AE08 FA03 FA07 FB06 FC02 4J002 CD021 CD051 DE136 FB280 FD016 FD096 FD140 FD150 GQ05 4J036 AA01 AA02 AD08 AJ08 DA01 DA02 DA05 DA06 DA09 DA10 DB06 DB15 DB21 DB22 DC02 DC25 DC26 DC46 DD07 EA05 FA02 FB07 HA07 JA07 4M109 AA01 BA04 CA04 CA12 EA02 EB20 EB02 EC18 EB20 EB14 EB20 EB08 EB18 EB08 EB08 EB08 EB09 EB08 EB08 EB08 EB08 EB08 EB08 EB09

Claims (8)

[Claims] 1. A resin composition for semiconductor encapsulation containing the following components (A) to (D). Masterbatch of (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) curing agent with black titanium oxide 2. A semiconductor encapsulating resin composition containing the following components (A) to (D). A filler masterbatch in which black titanium oxide is dispersed in (A) epoxy resin, (B) curing agent, (C) curing accelerator, and (D) phenolic curing agent in a particle size of 10 μm or less. , Black titanium oxide is a mixture of compounds represented by the general formula Ti _W O _X (1) (where W represents an integer of 1 to 3 and X represents a number of 1.0 to 7.0). The black titanium oxide is a phenolic curing agent that is solid at 25 ° C.
Hydroxyl equivalent of 50 g / eq, softening point of 50 to 120 ° C.,
And has a melting point of 45 to 250 ° C., and the amounts of the black titanium oxide and the phenolic curing agent are 5 to 70% by weight and 95 to 30% by weight, respectively, with respect to the total amount of the phenolic curing agent and the black titanium oxide. % Masterbatch of phenolic curing agent and black titanium oxide. 3. The black titanium oxide as the component (D) is TiO 2.
The resin composition for encapsulating a semiconductor according to claim 1 or 2, which is a mixture of Al and Ti ₂ O ₃ . 4. The black titanium oxide as the component (D) is Ti ₃
The resin composition for semiconductor encapsulation according to claim 1, which is a mixture of O ₅ and Ti ₄ O ₇ . 5. The resin composition for semiconductor encapsulation according to claim 1, wherein the component (C) is a latent curing accelerator. 6. The latent curing accelerator is a microcapsule type curing accelerator having a core / shell structure, and the core portion comprising the curing accelerator has a structural unit represented by the following general formula (1). Having polymer (However, each of R ₁ and R ₂ is a hydrogen atom or a monovalent organic group, and may be the same or different from each other.) As a main component and is covered with a shell portion. Item 6. A resin composition for semiconductor encapsulation according to Item 5. 7. A semiconductor device obtained by encapsulating a semiconductor element with the resin composition for encapsulating a semiconductor according to claim 1. 8. The semiconductor device according to claim 7, wherein the semiconductor device is a wafer level CSP, flip-chip type semiconductor device.