JP2007119598A - Semiconductor sealing epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor sealing epoxy resin composition which has good fluidity and curability in seal forming and has such good soldering resistance that no cracks are formed even in soldering at high temperatures coping with soldering with lead-free solder. <P>SOLUTION: Provided are a semiconductor sealing epoxy resin composition which is an epoxy resin composition comprising (A) an epoxy resin, (B) a phenolic resin, (C) an inorganic filler, (D) a cure accelerator, and (E) a coupling agent, wherein the cure accelerator (D) contains a cure accelerator (d1) having a cationic moiety and an anionic silicate moiety, and the coupling agent (E) comprises a secondary-amino-containing silane coupling agent (e1), and a semiconductor device prepared by sealing a semiconductor element therewith. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device using the same.

As a sealing method for semiconductor elements such as IC and LSI, transfer molding of an epoxy resin composition is suitable for mass production at low cost and has been adopted for a long time, and a phenol resin that is an epoxy resin or a curing agent in terms of reliability. Improvements have been made to improve the characteristics. However, due to the recent trend toward smaller, lighter, and higher performance electronic devices, semiconductors have been increasingly integrated and the surface mounting of semiconductor devices has been promoted. The demand for compositions has become increasingly severe. For this reason, the problem which cannot be solved with the conventional epoxy resin composition has also come out.
The biggest problem is that by adopting surface mounting, the semiconductor device is suddenly exposed to a high temperature of 200 ° C. or higher in the solder dipping or solder reflow process, and the moisture when moisture absorbed explosively evaporates. In particular, a phenomenon in which reliability is remarkably reduced due to peeling at the interface between various plated joints such as gold plating and silver plating on semiconductor elements, lead frames, and inner leads and the cured product of the epoxy resin composition. It is. In addition, with the shift from leaded solder to lead-free solder, which originated from environmental problems, the temperature during the soldering process increased, and the solder resistance due to explosive stress generated by the evaporation of moisture contained in the semiconductor device However, it has become a bigger problem than before.

  In order to improve reliability reduction due to solder processing, the amount of inorganic filler in the epoxy resin composition is increased to achieve low moisture absorption, high strength, and low thermal expansion of the cured product of the epoxy resin composition. In addition, there is a technique for improving the solder resistance of a semiconductor device and maintaining low viscosity and high fluidity at the time of molding an epoxy resin composition by using a low melt viscosity resin (for example, Patent Document 1). reference.). By using this method, the solder resistance of the cured product of the epoxy resin composition is considerably improved. However, as the filling ratio of the inorganic filler increases, the fluidity at the time of molding the epoxy resin composition is sacrificed, and the epoxy resin composition is cured. There was a drawback that the resin composition was not sufficiently filled in the package and voids were likely to occur. In addition, in order to prevent peeling at the interface between the plated part and the cured product of the epoxy resin composition, various coupling agents such as aminosilane and mercaptosilane are added to improve the fluidity during molding and the solder resistance of the cured product. Although a method for achieving both has been proposed (see, for example, Patent Document 2), an excellent epoxy resin composition for encapsulating a semiconductor capable of sufficiently satisfying both characteristics has not been obtained even by this method. . For this reason, there has been a demand for a further technique that satisfies the reliability of the semiconductor device without impairing the fluidity and filling property during molding even when the blending amount of the inorganic filler is increased.

JP 64-65116 (pages 1-7) Japanese Patent Laid-Open No. 9-255852 (pages 2-7)

  The present invention has been made in view of the above circumstances, and its purpose is to have good fluidity and curability at the time of sealing molding, and no cracks are generated even by high-temperature solder processing corresponding to lead-free solder. It is an object of the present invention to provide an epoxy resin composition for semiconductor encapsulation having good solder resistance and a highly reliable semiconductor device.

[1] In an epoxy resin composition containing (A) an epoxy resin, (B) a phenolic resin, (C) an inorganic filler, (D) a curing accelerator, and (E) a coupling agent, the curing accelerator (D ) Includes a curing accelerator (d1) having a cation portion and a silicate anion portion, and the coupling agent (E) includes a silane coupling agent having a secondary amino group. Resin composition,
[2] The epoxy resin composition for semiconductor encapsulation according to item [1], wherein the cation part of the curing accelerator (d1) having the cation part and the silicate anion part contains a phosphorus cation.
[3] The semiconductor encapsulation according to item [1] or [2], wherein the curing accelerator (d1) having the cation part and the silicate anion part is a compound represented by the following general formula (1): Epoxy resin composition for

（ただし、上記一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ^１は、置換基Ｙ^１およびＹ^２と結合する有機基である。式中Ｘ^２は、置換基Ｙ^３およびＹ^４と結合する有機基である。Ｙ^１およびＹ^２はプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の置換基Ｙ^１、およびＹ^２が珪素原子と結合してキレート構造を形成するものである。Ｙ^３およびＹ^４はプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の置換基Ｙ^３およびＹ^４が珪素原子と結合してキレート構造を形成するものである。Ｘ^１、およびＸ^２は互いに同一でも異なっていてもよく、Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４は互いに同一であっても異なっていてもよい。Ｚ^１は置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表す。）

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. In the formula, X ¹ is an organic group bonded to the substituents Y ¹ and Y ^{2. In the} formula, X ² represents the substituents Y ³ and Y ⁴ and Y ¹ and Y ² are groups formed by proton-donating substituents releasing protons, and the substituents Y ¹ and Y ² in the same molecule are bonded to a silicon atom to form a chelate structure. Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule bind to a silicon atom to form a chelate structure. and forms .X ^1, and ^{X 2} May be the same or different from each ^{other, Y 1, Y 2, Y} 3, and Y ⁴ may .Z ¹ also being the same or different organic having a substituted or unsubstituted aromatic or heterocyclic ring Represents a group, or a substituted or unsubstituted aliphatic group.)

[4] A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition for semiconductor sealing according to any one of [1] to [3],
It is.

  According to the present invention, a semiconductor encapsulant having good fluidity and curability at the time of sealing molding of a semiconductor element and the like and having good solder resistance that does not generate cracks even by high-temperature solder processing corresponding to lead-free solder. An epoxy resin composition for stopping is obtained.

The present invention includes an epoxy resin, a phenolic resin, an inorganic filler, a curing accelerator having a cation part and a silicate anion part, and a silane coupling agent having a secondary amino group as essential components, thereby providing a semiconductor element, etc. An epoxy resin composition for semiconductor encapsulation having good fluidity and filling properties at the time of sealing molding and having good solder resistance with no cracks generated even by high-temperature soldering treatment corresponding to lead-free solder is obtained. It is what
Hereinafter, the present invention will be described in detail.

  The epoxy resin (A) used in the present invention is a monomer, oligomer, or polymer in general having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Resin, bisphenol type epoxy resin, stilbene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified Phenol type epoxy resin, phenol aralkyl type epoxy resin (having phenylene skeleton, biphenylene skeleton, etc.), sulfur atom containing type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthol alla Kill epoxy resin (phenylene skeleton, a biphenylene skeleton, etc.), and the like. These no problem be used singly or in admixture.

  The phenolic resin (B) used in the present invention is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak Resin, cresol novolac resin, dicyclopentadiene modified phenol resin, terpene modified phenol resin, triphenolmethane type resin, phenol aralkyl resin (having phenylene skeleton, biphenylene skeleton, etc.), sulfur atom-containing phenol resin, naphthol novolak resin, naphthol Examples thereof include aralkyl resins (having a phenylene skeleton, a biphenylene skeleton, and the like), and these may be used alone or in combination.

  As the blending amount of the epoxy resin (A) and the phenolic resin (B) used in the present invention, the ratio of the number of epoxy groups of all epoxy resins to the number of phenolic hydroxyl groups of all phenolic resins is 0.7 or more and 1.3 or less. It is preferable that Within this range, a decrease in curability of the epoxy resin composition, a decrease in glass transition temperature of the cured product, a decrease in moisture resistance reliability, and the like can be suppressed.

As an inorganic filler (C) used for this invention, what is generally used for the epoxy resin composition for semiconductor sealing can be used. Examples thereof include fused silica, crystalline silica, talc, alumina, silicon nitride and the like, and the most preferably used is spherical fused silica. These inorganic fillers may be used alone or in combination. The maximum particle size of the inorganic filler (C) is not particularly limited, but is 105 μm or less in consideration of prevention of defects such as wire deformation caused by sandwiching coarse particles of the inorganic filler between narrow wires. It is preferable that it is 75 μm or less.
Although content of an inorganic filler (C) is not specifically limited, 80 weight% or more and 94 weight% or less are preferable in all the epoxy resin compositions. Within this range, a decrease in solder resistance, a decrease in fluidity, and the like can be suppressed.

（ただし、上記一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表し、互いに同一であっても異なっていてもよい。式中Ｘ^１は、置換基Ｙ^１およびＹ^２と結合する有機基である。式中Ｘ^２は、置換基Ｙ^３およびＹ^４と結合する有機基である。Ｙ^１およびＹ^２はプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の置換基Ｙ^１、およびＹ^２が珪素原子と結合してキレート構造を形成するものである。Ｙ^３およびＹ^４はプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の置換基Ｙ^３およびＹ^４が珪素原子と結合してキレート構造を形成するものである。Ｘ^１、およびＸ^２は互いに同一でも異なっていてもよく、Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４は互いに同一であっても異なっていてもよい。Ｚ^１は置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を表す。） The curing accelerator (D) used in the present invention includes a curing accelerator (d1) having a cation part that can accelerate the curing reaction of the epoxy resin and a silicate anion part that suppresses the activity that accelerates the curing reaction. Is essential. As a hardening accelerator (d1) which has a cation part and a silicate anion part, what a cation part contains a phosphorus cation is preferable, and the compound represented by following General formula (1) is more preferable.

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. In the formula, X ¹ is an organic group bonded to the substituents Y ¹ and Y ^{2. In the} formula, X ² represents the substituents Y ³ and Y ⁴ and Y ¹ and Y ² are groups formed by proton-donating substituents releasing protons, and the substituents Y ¹ and Y ² in the same molecule are bonded to a silicon atom to form a chelate structure. Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule bind to a silicon atom to form a chelate structure. and forms .X ^1, and ^{X 2} May be the same or different from each ^{other, Y 1, Y 2, Y} 3, and Y ⁴ may .Z ¹ also being the same or different organic having a substituted or unsubstituted aromatic or heterocyclic ring Represents a group, or a substituted or unsubstituted aliphatic group.)

In the general formula (1), examples of the substituents R ^{1 to} R ⁴ include a phenyl group, a methylphenyl group, a methoxyphenyl group, a hydroxyphenyl group, a naphthyl group, a hydroxynaphthyl group, a benzyl group, a methyl group, and an ethyl group. , N-butyl group, n-octyl group, cyclohexyl group, etc., among these, substituted or unsubstituted aromatic groups such as phenyl group, methylphenyl group, methoxyphenyl group, hydroxyphenyl group, hydroxynaphthyl group, etc. Is more preferable.
Further, in the general formula (1), the substituent ^{X 1} is an organic group bonding to the substituent ^{Y 1} and ^{Y 2.} Similarly, the substituent X ² is an organic group bonded to the substituents Y ³ and Y ⁴ . Substituents Y ¹ and Y ² is a group proton donating substituent group releases a proton, those substituents Y ¹ in the same ^molecule, and the Y ² are linked with the silicon atom to form a chelate structure is there. Similarly, the substituents Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule bind to a silicon atom to form a chelate structure. Is. The substituents X ¹ and X ² may be the same or different from each other, and the substituents Y ¹ , Y ² , Y ³ , and Y ⁴ may be the same or different from each other.
Such a group represented by Y ¹ X ¹ Y ² and Y ³ X ² Y ⁴ in the general formula (1) is composed of a group formed by releasing two protons from a bivalent or higher proton donor. Examples of divalent or higher proton donors include catechol, pyrogallol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2'-biphenol, 1,1'-bi- 2-naphthol, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid, 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol and Among them, catechol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene are more preferable. preferable.

  Although the compounding quantity of the hardening accelerator (d1) which has a cation part and a silicate anion part used by this invention is not specifically limited, 0.1 weight% or more and 1.5 weight% or less are in all the epoxy resin compositions. Desirably, more preferably 0.2 wt% or more and 1 wt% or less. Within the above range, the viscosity of the epoxy resin composition can be reduced, the fluidity can be increased, and the storage stability during storage can be improved.

  In the present invention, as long as the effect of using the curing accelerator (d1) having a cation part and a silicate anion part is not impaired, a curing accelerator other than the curing accelerator (d1) may be an epoxy group and a phenol. As long as it promotes the reaction of the reactive hydroxyl group, it can be used in combination without any particular limitation, but the blending ratio of the curing accelerator (d1) having a cation silicate anion moiety is 50% by weight with respect to the total curing accelerator (D). The above is preferable. Examples of curing accelerators that can be used in combination include adducts of phosphine compounds and quinone compounds; diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof; tributylamine, benzyl Amine compounds such as dimethylamine; imidazole compounds such as 2-methylimidazole; organic phosphines such as triphenylphosphine and methyldiphenylphosphine; tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrakis (benzoyloxy) borate, tetra Examples thereof include tetra-substituted phosphonium / tetra-substituted borates such as phenylphosphonium / tetrakis (naphthoyloxy) borate, and these may be used alone or in combination of two or more.

  It is essential that the coupling agent (E) used in the present invention contains a silane coupling agent (e1) having a secondary amino group. Although it does not specifically limit as a silane coupling agent (e1) which has a secondary amino group, For example, N-phenyl gamma-aminopropyl trimethoxysilane, N-phenyl gamma-aminopropyl triethoxysilane, N- Phenyl γ-aminopropylmethyldimethoxysilane, n-butylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, amino p-xylylene γ-aminopropyltrimethoxysilane and the like may be mentioned, and these may be used alone or in combination of two or more. The compounding amount of the silane coupling agent (e1) having a secondary amino group is not particularly limited, but is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.05% by weight in the total epoxy resin composition. % To 0.8% by weight. Within the above range, it is possible to achieve low viscosity and high fluidity during the molding of the epoxy resin composition, and it is possible to suppress a decrease in curability of the epoxy resin composition. In addition, these silane coupling agents may be used after being hydrolyzed by adding water or an acid or an alkali as necessary, or may be previously treated with an inorganic filler.

  In the epoxy resin composition of the present invention, a coupling agent other than the silane coupling agent (e1) having a secondary amino group can be used in combination as necessary. Examples of coupling agents that can be used in combination include coupling agents other than silane coupling agents such as titanate coupling agents, aluminum coupling agents, aluminum / zirconium coupling agents, primary aminosilanes, mercaptosilanes, epoxysilanes, Examples include silane coupling agents such as alkyl silane, ureido silane, and vinyl silane. Specific examples of these include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropi Triethoxysilane, vinyltriethoxysilane and the like. These may be used in combination one kind alone or two or more kinds may.

  The present invention relates to a curing accelerator (d1) having a cation moiety that can accelerate the curing reaction of an epoxy resin and a silicate anion moiety that suppresses the activity that accelerates the curing reaction, and a silane coupling agent having a secondary amino group. (E1) is used in combination to express its synergistic effect. By using these two types in combination, the latent period until the reaction starts is prolonged, the fluidity is extended, and the reaction is fast until the end of the reaction.

  The epoxy resin composition of the present invention includes an epoxy resin, a phenol resin, an inorganic filler, a curing accelerator including a curing accelerator having a cation portion and a silicate anion portion, and a silane coupling agent having a secondary amino group. Coupling agent is an essential component, but if necessary, release agent; hydrotalcite, ion trapping agent such as hydrous oxide of elements selected from magnesium, aluminum, bismuth, titanium, zirconium; silicone oil Low stress additives such as rubber, adhesion imparting agents such as thiazoline, diazole, triazole, triazine, pyrimidine; brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, etc. Additives such as flame retardants may be added as appropriate There.

The epoxy resin composition of the present invention is obtained by mixing the raw materials sufficiently uniformly using a mixer or the like, then melt-kneading with a hot roll or kneader, etc., cooling and pulverizing.
The epoxy resin composition of the present invention is used to encapsulate various electronic components such as semiconductor elements, and to manufacture semiconductor devices by conventional molding methods such as transfer molding, compression molding, and injection molding. do it.

Examples of the present invention are shown below, but the present invention is not limited thereto. The blending ratio is parts by weight.
In addition, it shows below about the content of the hardening accelerator used by the Example and the comparative example.

Curing accelerator 1: Compound represented by the following chemical formula (2)

Curing accelerator 2: Compound represented by the following chemical formula (3)

Curing accelerator 3: Compound represented by the following chemical formula (4)

Curing accelerator 4: Compound represented by the following chemical formula (5)

Curing accelerator 5: Compound represented by the following chemical formula (6)

Curing accelerator 6: Compound represented by the following chemical formula (7)

Curing accelerator 7: Compound represented by the following chemical formula (8)

Here, as an example, a method for synthesizing the curing accelerator 1 will be described, but the present invention is not limited thereto.
In a flask containing 1800 g of methanol, 249.5 g of phenyltrimethoxysilane and 384.0 g of 2,3-dihydroxynaphthalene were added and dissolved, and then 231.5 g of 28% sodium methoxide-methanol solution was added dropwise with stirring at room temperature. Furthermore, when a solution prepared by dissolving 503.0 g of tetraphenylphosphonium bromide prepared in advance in 600 g of methanol was added dropwise with stirring at room temperature, crystals were deposited. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a pinkish white crystal curing accelerator 1.

Example 1
Epoxy resin 1: phenol aralkyl type epoxy resin having a biphenylene skeleton represented by the following formula (9) (Nippon Kayaku Co., Ltd., trade name: NC3000P, softening point: 58 ° C., epoxy equivalent: 273) 66 parts by weight

Phenol resin 1: phenol aralkyl resin having a biphenylene skeleton represented by the following formula (10) (Maywa Kasei Co., Ltd., trade name MEH-7851SS, softening point 107 ° C., hydroxyl group equivalent 204) 40 parts by weight

Fused spherical silica 1: (average particle size 22 μm, specific surface area 3.0 m ² / g)
780 parts by weight Fused spherical silica 2: (average particle size 0.5 μm, specific surface area 6.0 m ² / g)
100 parts by weight Curing accelerator 1 5 parts by weight Coupling agent 1: N-phenyl γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-573) 3 parts by weight Carnauba wax (Nikko Fine Products Co., Ltd.) ) Product name Nikko Carnauba)
3 parts by weight Carbon black: (Mitsubishi Chemical Co., Ltd., trade name MA-600) 3 parts by weight was mixed in a mixer, kneaded at 95 ° C. for 8 minutes using a hot roll, cooled, pulverized, and epoxy A resin composition was obtained. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.

Evaluation method Spiral flow: Using a low-pressure transfer molding machine, a spiral flow measurement mold conforming to EMMI-1-66, with a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 120 seconds. The resin composition was injected and the flow length was measured.

  Reaction start time: The time at which the torque value rose after starting measurement at 175 ° C. using a curast meter (Orientec Co., Ltd., JSR curast meter IVPS type) is shown.

  Reaction end time: The time from when the torque rises with a curast meter until 90% of the torque value after 300 seconds is shown.

  Solder resistance: Using a low-pressure transfer molding machine, 80pQFP (Cu frame, chip size 6.0 mm × 6.0 mm) was molded at a molding temperature of 175 ° C., a pressure of 8.3 MPa, and a curing time of 120 seconds. Heat treatment was performed at 175 ° C. for 8 hours. Then, after performing the humidification process for 120 hours at 85 degreeC and 85% of relative humidity, IR reflow process of 260 degreeC was performed. Peeling and cracks inside the package were confirmed with an ultrasonic flaw detector. The number of defective packages among the 10 packages is shown.

Examples 2-6, Comparative Examples 1-7
According to the composition of Table 1 and Table 2, an epoxy resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.
The raw materials used other than Example 1 are shown below.
Epoxy resin 2: biphenyl type epoxy resin represented by the following formula (11) (product name YX-4000, epoxy equivalent 190, melting point 105 ° C., manufactured by Japan Epoxy Resin Co., Ltd.)

Phenol resin 2: Phenol aralkyl resin represented by the following formula (12) (Mitsui Chemicals, trade name: XLC-LL, hydroxyl group equivalent: 165, softening point: 79 ° C.)

Coupling agent 2: n-butyl γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X12-806)
Coupling agent 3: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-403)
Coupling agent 4: γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903)

Each of Examples 1 to 4 uses both the curing accelerator (d1) having a cation portion and a silicate anion portion and the silane coupling agent (e1) having a secondary amino group according to the present invention. However, regardless of the type of the curing accelerator (d1) having a cation part and a silicate anion part and the kind of the silane coupling agent (e1) having a secondary amino group, It exhibited an ideal fluid hardening behavior that is high fluidity due to its long length, and has good curability due to its fast time to completion of the reaction. Moreover, also in Example 5 which changed the kind of epoxy resin and hardening | curing agent, and the compounding quantity of the inorganic filler, the favorable fluid hardening behavior according to Examples 1-4 was shown. Moreover, all Examples 1-5 showed favorable solder resistance. On the other hand, although the curing accelerator (d1) having a cation portion and a silicate anion portion is used, the reaction starts in Comparative Examples 1 to 3 in which the silane coupling agent (e1) having a secondary amino group is not used. As a result, the flow time decreased and the fluidity decreased, and conversely, the time until the reaction reached the end increased and the curability decreased. Moreover, in Comparative Examples 4-7 which did not use the hardening accelerator (d1) which has a cation part and a silicate anion part, time until reaction started further became short, fluidity | liquidity fell significantly, and reaction was carried out conversely As a result, the time until the end of the process was further increased, and the curability was greatly reduced. Furthermore, Comparative Example 1 and Comparative Examples 4 to 7 resulted in poor solder resistance.
As described above, Examples 1 to 5 according to the present invention show good fluidity and curability at the time of molding, and show good solder resistance that does not cause cracks even by high-temperature solder processing corresponding to lead-free solder. As a result.

  According to the present invention, the epoxy resin for semiconductor encapsulation has good fluidity and curability at the time of sealing molding, and has good solder resistance that does not generate cracks even by high-temperature solder processing corresponding to lead-free solder. A composition and a highly reliable semiconductor device can be provided.

Claims (4)

In the epoxy resin composition containing (A) an epoxy resin, (B) a phenolic resin, (C) an inorganic filler, (D) a curing accelerator, and (E) a coupling agent, the curing accelerator (D) is a cation. Epoxy for semiconductor encapsulation, characterized by comprising a curing accelerator (d1) having a part and a silicate anion part, and wherein the coupling agent (E) comprises a silane coupling agent (e1) having a secondary amino group Resin composition. The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the cation part of the curing accelerator (d1) having the cation part and the silicate anion part contains a phosphorus cation. The epoxy resin composition for semiconductor encapsulation according to claim 1 or 2, wherein the curing accelerator (d1) having the cation part and the silicate anion part is a compound represented by the following general formula (1).

(In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. In the formula, X ¹ is an organic group bonded to the substituents Y ¹ and Y ^{2. In the} formula, X ² represents the substituents Y ³ and Y ⁴ and Y ¹ and Y ² are groups formed by proton-donating substituents releasing protons, and the substituents Y ¹ and Y ² in the same molecule are bonded to a silicon atom to form a chelate structure. Y ³ and Y ⁴ are groups formed by proton-donating substituents releasing protons, and the substituents Y ³ and Y ⁴ in the same molecule bind to a silicon atom to form a chelate structure. and forms .X ^1, and ^{X 2} May be the same or different from each ^{other, Y 1, Y 2, Y} 3, and Y ⁴ may .Z ¹ also being the same or different organic having a substituted or unsubstituted aromatic or heterocyclic ring Represents a group, or a substituted or unsubstituted aliphatic group.) A semiconductor device comprising a semiconductor element sealed using the epoxy resin composition for semiconductor sealing according to any one of claims 1 to 3.